Diversity in electrochemical oxidation of dihydroxybenzenes in the ...

Indian Academy of Sciences (India)

Abstract. Electrochemical oxidation of some catechol derivatives (1a–e) have been studied in water/ acetonitrile solution containing 1-methylindole (3) as a nucleophile, using cyclic voltammetry and controlled- potential coulometry. An interesting diversity in the mechanisms has been observed in electrochemical oxidation ...

Uranium coulometric titration. Application to the determination of traces

International Nuclear Information System (INIS)

Bergey, C.

After a description of the device, the means developed to improve the titration method are presented. Coulometry enables to determine U with an accuracy of 0,1% in samples of only several tenths of a milligram. This method is rapid but not intended for routine analysis [fr

Plutonium oxides and uranium and plutonium mixed oxides. Carbon determination

International Nuclear Information System (INIS)

Anon.

Determination of carbon in plutonium oxides and uranium plutonium mixed oxides, suitable for a carbon content between 20 to 3000 ppm. The sample is roasted in oxygen at 1200 0 C, the carbon dioxide produced by combustion is neutralized by barium hydroxide generated automatically by coulometry [fr

Determination of plutonium by secondary coulometric titration with internally generated iron(II) Pt. 2

International Nuclear Information System (INIS)

Chitnis, R.T.; Talnikar, S.G.; Thakur, V.A.; Paranjape, A.H.

1979-01-01

Determination of plutonium by secondary coulometry involving the controlled potential technique for the generation of an iron(II) mediator, is reported in Part I. In this paper, the same determination is reported using constant current coulometry for the generation of the mediator, and zero current potentiometry for end-point detection. The factors affecting the current efficiency, viz. current density and supporting electrolyte composition have been checked in order to define the appropriate conditions for obtaining 100% current efficiency. The original method of Carson et al. suffers from the disadvantage that it involves complicated sample treatment. Introduction of perchloric acid treatment as a method for the oxidation of plutonium and the pretitration of the supporting electrolyte to the end-point potential prior to sample addition, have considerably helped to improve the precision and accuracy of the method. Exhaustive analytical data are reported covering plutonium quantities ranging from 25 micrograms to 5 milligrams, which establishes the scope of the method. (author)

Electrochemical Studies on New Chelating Compounds of the Mono- and Bis(Imidazolyl) Pyridine Type

Czech Academy of Sciences Publication Activity Database

Mikysek, T.; Švancara, I.; Bartoš, M.; Vytřas, K.; Drabina, P.; Sedlák, M.; Klíma, Jiří; Urban, Jiří; Ludvík, Jiří

2007-01-01

Roč. 19, č. 24 (2007), s. 2529-2537 ISSN 1040-0397 R&D Projects: GA MŠk LC510; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z40400503 Keywords : voltammetry * polarography * coulometry Subject RIV: CG - Electrochemistry Impact factor: 2.949, year: 2007

An automated instrument for controlled-potential coulometry: System documentation

Energy Technology Data Exchange (ETDEWEB)

Holland, M K; Cordaro, J V

1988-06-01

An automated controlled-potential coulometer has been developed at the Savannah River Plant for the determination of plutonium. Two such coulometers have been assembled, evaluated, and applied. The software is based upon the methodology used at the Savannah River Plant, however the system is applicable with minimal software modifications to any of the methodologies used throughout the nuclear industry. These state-of-the-art coulometers feature electrical calibration of the integration system, background current corrections, and control-potential adjustment capabilities. Measurement precision within 0.1% has been demonstrated. The systems have also been successfully applied to the determination of pure neptunium solutions. The design and documentation of the automated instrument are described herein. Each individual module's operation, wiring layout, and alignment are described. Interconnection of the modules and system calibration are discussed. A complete set of system prints and a list of associated parts are included. 9 refs., 10 figs., 6 tabs.

Methods for the accountability of uranium dioxide

International Nuclear Information System (INIS)

Stephens, F.B.; Gutmacher, R.G.; Ernst, K.; Harrar, J.E.; Turel, S.P.

1975-06-01

Procedures for the determination of the total U and the amount of 235 U isotope in UO 2 powder and pellets are given. Methods for U determination include coulometry, titration, and gravimetry. Surface-ionization mass spectroscopy is described for 235 U measurement. Spectrometric procedures are described for determining the impurity content in the UO 2 . (U.S.)

Study of the mechanism and kinetics of the reduction of uranyl ions in phosphoric acid solutions

International Nuclear Information System (INIS)

El Kacemi, K.; Tyburce, B.; Belcadi, S.

1982-01-01

The electrochemical reduction of uranyl ions in 0.1 to 9 M phosphoric acid has been investigated by polarography, cyclic voltammetry, chronopotentiometry and potentiostatic coulometry. In concentrated phosphoric acid solutions (H 3 PO 4 3 PO 4 concentrations. So, when the concentration of U(VI) increases and/or that of H 3 PO 4 reduces, the system becomes reversible. (author)

Spectroelectrochemical determination of the electron consumption

Czech Academy of Sciences Publication Activity Database

Kolivoška, Viliam; Gál, Miroslav; Lachmanová, Štěpánka; Valášek, Michal; Hromadová, Magdaléna; Pospíšil, Lubomír

2011-01-01

Roč. 697, 1-2 (2011), s. 23-26 ISSN 0003-2670 R&D Projects: GA ČR GA203/09/0705; GA AV ČR IAA400400802; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : coulometry * spectroelectrochemistry * elecrolysis Subject RIV: CG - Electrochemistry Impact factor: 4.555, year: 2011

Studies on preparation of some alkaloid complexes and solvent extraction

International Nuclear Information System (INIS)

Mohamed, A.A.

1989-01-01

Describes the various methods available in the literature for the determination of different classes of alkaloids spectrochemical (e.g.spectrophotometry and colorimetry, fluorimetry and phosphorimetry, nephelometry and reiractometry), electrochemical (e.g. polarography, amperometry, conductometry, coulometry and potentiometry), volumetric (e.q. acid-base, iodometry , bromimetry , oxidimetry, complexometry and precipitation ) and miscellaneous methods (e.g.gasliquid chromatography, gravimetry, thermometry and rediometry ) has been discussed

Monitoring of fluoride and iodide levels in drinking water using ion selective electrodes

International Nuclear Information System (INIS)

Ahmed, R.; Viqar-Un-Nisa; Hussain, M.; Tanwir, R.; Qureshi, S.A.

2004-01-01

Fluoride and iodide, the most important constituents of drinking water are essential as well as toxic depending on their levels. For their analysis in water mostly ion-selective electrodes, spectrophotometry, titrimetry and coulometry etc; have been used and literature has been briefly reviewed. Ion-selective electrodes offer an efficient method for the measurement of the two halides and were mostly used during this work. Fabrication of these electrodes is briefly described. Comparison of results obtained by ion selective electrode and coulometry is given. Recoveries of the added fluoride ions from the samples were good. A large number of water samples from Rawalpindi-Islamabad area were analyzed for fluoride and iodide. Levels of fluoride and iodide from two main water reservoirs of Rawalpindi and Islamabad are reported before and after treatment. Both surface and ground water samples were analyzed and results are compared and discussed. Some samples from northern areas were also analyzed for iodide and fluoride and compared. Intake of fluoride and iodide from water of different areas is also compared. Water samples, which caused bone deformation in certain areas in Punjab due to excess fluoride, were also analyzed for fluoride and results are presented. (author)

Chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade mixed oxides [(U,Pu)O2

International Nuclear Information System (INIS)

Anon.

1981-01-01

Mixed oxide, a mixture of uranium and plutonium oxides, is used as a nuclear-reactor fuel in the form of pellets. The plutonium content may be up to 10 wt %, and the diluent uranium may be of any U-235 enrichment. In order to be suitable for use as a nuclear fuel, the material must meet certain criteria for combined uranium and plutonium content, effective fissile content, and impurity content. Analytical procedures used to determine if mixed oxides comply with specifications are: uranium by controlled-potential coulometry; plutonium by controlled-potential coulometry; plutonium by amperometric titration with iron (II); nitrogen by distillation spectrophotometry using Nessler reagent; carbon (total) by direct combustion-thermal-conductivity; total chlorine and fluorine by pyrohydrolysis; sulfur by distillation-spectrophotometry; moisture by the coulometric, electrolytic moisture analyzer; isotopic composition by mass spectrometry; rare earths by copper spark spectroscopy; trace impurities by carrier distillation spectroscopy; impurities by spark-source mass spectrography; total gas in reactor-grade mixed dioxide pellets; tungsten by dithiol-spectrophotometry; rare earth elements by spectroscopy; plutonium-238 isotopic abundance by alpha spectrometry; uranium and plutonium isotopic analysis by mass spectrometry; oxygen-to-metal atom ratio by gravimetry

PC based controlled potential coulometric titrator for quantitative analysis of nuclear materials

International Nuclear Information System (INIS)

Manna, A.; Moorthy, A.D.; Bhogale, R.G.

2001-01-01

With increased requirements for process control and accountability of nuclear materials in plutonium reprocessing plants, the PC based controlled potential coulometric titrator was developed which has the capability of automatic quantitative analysis of the samples. The instruments based on electromechanical methods, incorporates an electronic potentiostat, a digital coulometer with wide dynamic range and a PC with a control interface card. The potentiostat is required to control the potential at the working electrode surface as per predetermined controlled voltage with respect to a reference electrode under wide variations in the conductivity and double layer capacitance of the electrochemical cell. The digital coulometer precisely measures the amount of electronic charge taking part in the electrochemical reactions of interest. The software has the facility to carry out three different types of analysis, i.e., primary coulometry, secondary coulometry and coulogram curve tracing. Due to complete analysis of the samples under program control, the human related errors are minimized and a better precision in the results are obtained. It has been possible to obtain an overall precession of better than +/- 0.3% in the determination of plutonium using the instrument. (author)

Preparation procedure and certification of uranous-uranic oxide and nitric acid solution of neptunium as standard specimens of plant

International Nuclear Information System (INIS)

Bulyanitsa, L.S.; Lipovskij, A.A.; Ryzhinskij, M.V.; Preobrazhensskaya, L.D.; Aleksandruk, V.M.; Alekseeva, N.A.; Gromova, E.A.; Solntseva, L.F.; Shereshevskaya, I.I.

1981-01-01

Two techniques of certification of standard specimens of plant (SSP) are considered. The first technique-comparison with initial SS-metallic uranium NBS-960 - is used for certification of uranium. protoxide-oxide. The mass part of the sum of analyzed impurities in prepared initial SS is (8.4+-0.8)x10 -3 %. For certification according to mass uranium part the method of gravimetric potentiometric titration with semiautomatic titrator is used; the mean quadratic deviation of the method is s=0.0002-0.0003, certified value of uranium mass part in SSP (taking account of the error of initial SS) is (84.80+-0.02)%. The second technigue - a simplified circular experiment - is used for certification of SSP-nitric acid solution of neptunium as to Np mass part. Coulometry at controlled potential and coulometry at controlled current and two variants of potentiometric titration are used as certification methods of analysis. Relative mean quadratic deviations of the methods are ssub(r)=0.0014-0.0023. When calculating total error of certified value of neptunium mass part constituents of both accidental and unremoved systematic errors of the methods were included. The final certification result of SSP is (5.707+-0.018)% [ru

Positron implantation studies of YBa2Cu3O7-x

International Nuclear Information System (INIS)

Anwand, W.; Brauer, G.; Coleman, P.G.; Knights, A.P.; Teske, K.; Schuster, G.; Rudolph, K.

1995-01-01

Slow positron implantation spectroscopy has been applied to the study of a set of samples of superconducting YBa 2 Cu 3 O 7-x . The depth-sensitive positron response to oxygen content and preparation history is presented. An outline is given of the experimental method - solid electrolyte coulometry in carrier-gas mode - used to measure oxygen exchange for the same set of samples. (orig.)

Studies on preparation of some alkaloid complexes and solvent extraction

Energy Technology Data Exchange (ETDEWEB)

Mohamed, A A

1990-12-31

Describes the various methods available in the literature for the determination of different classes of alkaloids spectrochemical (e.g.spectrophotometry and colorimetry, fluorimetry and phosphorimetry, nephelometry and reiractometry), electrochemical (e.g. polarography, amperometry, conductometry, coulometry and potentiometry), volumetric (e.q. acid-base, iodometry , bromimetry , oxidimetry, complexometry and precipitation ) and miscellaneous methods (e.g.gasliquid chromatography, gravimetry, thermometry and rediometry ) has been discussed. 31 tabs; 29 figs; 402 refs.

Electrochemical Study of Bromide in the Presence of 1,3-Indandione. Application to the Electrochemical Synthesis of Bromo Derivatives of 1,3-Indandione

OpenAIRE

Nematollahi, D.; Akaberi, N.

2001-01-01

The electrochemical oxidation of bromide in the presence of 1,3-indandione (1) in water/acetic acid and methanol/acetic acid mixtures has been studied by cyclic voltammetry and controlled-potential coulometry. The results indicate the participation of 1,3-indandione in the bromination reaction. On the basis of the electroanalytical and preparative results a reaction mechanism including electron transfer, chemical reaction and regeneration of bromide was discussed. The electrochemical synthesi...

Organic matter - A key factor in controlling mercury distribution in estuarine sediment

Digital Repository Service at National Institute of Oceanography (India)

Chakraborty, P.; Sarkar, A.; Vudamala, K.; Naik, R.; Nath, B.N.

were analyzed for total carbon (TC), total inorganic carbon (TIC), total nitrogen (TN) content. TC and TN in sediments were determined using Flash 2000 CHN-elemental analyzer (Thermo Fisher Scientific Incorporation). Precision of the analysis... was within ± 5 %. Soil NC was used as certified reference material. TIC was determined by coulometry (UIC coulometrics). Anhydrated calcium carbonate was used as standard material. Relative standard deviation of the analysis was within ± 2 %. Total organic...

Voltammetry and coulometry of indium in two-side thin-layer system

International Nuclear Information System (INIS)

Eliseeva, L.V.; Kabanova, O.L.

1980-01-01

An electrochemical behaviour of In and possibilities for its determination have been investigated, using halide background solutions, by voltametry in the thin solution layer thin mercury film system. It has been shown that the maximum current of indium (3) is directly proportional to its concentration over a range of 1x10 -4 - 5x10 -3 M and the maximum current of indium oxidation from the amalgam over a range of 5x10 -7 - 1x10 -4 M. Examined were the effects of halide ion concentration, pH, electrode potential change rate on current maximum value, product efficiency of reducing indium (3) and oxidizing its amalgam, on maximum current potential and half-peak width. The analytical signal has been found to be directly proportional to chloride ion concentration over a range of 0.1 - 3.0 M, bromide and iodide ion concentration over a range of 0.1 - 1.0 M. This makes it possible to use the method for determination of halide ions

Precision determination of uranium in uranium oxide by constant-current coulometry

International Nuclear Information System (INIS)

Xu Laili; Wang Chunhuan.

1990-01-01

A method of constant-current coulometric titration for determination of uranium in uranium oxide is described. This method involves preliminary reduction of U (VI) in H 2 SO 4 -H 3 PO 4 medium by Cr (II) as a reductant, followed by air oxidation of excess of Cr (II), addition of solid K 2 Cr 2 O 7 in quantity slightly more than that of the required for quantitative oxidation of U (IV) and final titration of excess of K 2 Cr 2 O 7 with the electrogenerated Fe (II). The endpoint is determined amperometrically. The effect of various factors on the sample treatment and reduction-oxidation processes has been examined. The precision of the method as indicated by the standard deviation of an individual observation is less than 0.01% for l gram uranium oxide

Coulometry and Calorimetry of Electric Double Layer Formation in Porous Electrodes

NARCIS (Netherlands)

Janssen, Mathijs; Griffioen, Elian; Biesheuvel, P. M.; Van Roij, René; Erné, Ben

2017-01-01

Coulometric measurements on salt-water-immersed nanoporous carbon electrodes reveal, at a fixed voltage, a charge decrease with increasing temperature. During far-out-of-equilibrium charging of these electrodes, calorimetry indicates the production of both irreversible Joule heat and reversible

Lithium cell reactions. Interim report, December 1981-May 1983. [Lithium-thionyl chloride cell

Energy Technology Data Exchange (ETDEWEB)

Clark, W.; Dampier, F.; Lombardi, A.; Cole, T.

1983-12-01

This report presents the results of a program that investigated reactions occurring in lithium-thionyl chloride cells for a range of specified test conditions and also performed detailed analyses for impurities present in cell components, assessed the impact of each impurity on cell performance and safety, and recommended concentration limits for detrimental impurities. Methods used in the program included linear sweep voltammetry, constant current coulometry, infrared spectroscopy, chemical analysis of the reagents and cell components, and cell discharge tests.

Probing anodic oxidation kinetics and nanoscale heterogeneity within TiO2 films by Conductive Atomic Force Microscopy and combined techniques

International Nuclear Information System (INIS)

Diamanti, M.V.; Souier, T.; Stefancich, M.; Chiesa, M.; Pedeferri, M.P.

2014-01-01

Graphical abstract: - Highlights: • Nanoscale anodic titanium oxides were investigated with multidisciplinary approach. • Oxide thickness was estimated via spectrophotometry and coulometry. • C-AFM identified nanometric conductivity heterogeneities, ascribed to oxide structure. • High conductivity areas exhibited local memristive behavior. - Abstract: Anodic oxidation of titanium in acid electrolytes allows to obtain a thin, compact oxide layer with thickness, structure, color, and electrical properties that vary with process parameters imposed, among which cell voltage has a key effect. Although oxidation kinetics have been investigated in several research works, a broader vision of oxide properties–including thickness and structure–still has to be achieved, especially in the case of very thin oxide films, few tens of nanometers thick. This is vital for engineered applications of nanostructured TiO 2 films, as in the field of memristive devices, where a precise control of oxide thickness, composition and structure is required to tune its electrical response. In this work, oxide films were produced on titanium with thickness ranging from few nanometers to 200 nm. Oxide thickness was estimated by coulometry and spectrophotometry. These techniques were then combined with C-AFM, which provided a deeper understanding of oxide thickness and uniformity of the metal surface and probed the presence of crystalline nano-domains within the amorphous oxide phase affecting the overall film electrical and optical properties

Nonenzymatic glucose sensing based on deposited palladium nanoparticles on epoxy-silver electrodes

International Nuclear Information System (INIS)

Gutes, Albert; Carraro, Carlo; Maboudian, Roya

2011-01-01

Highlights: → New nonenzymatic glucose sensor material. → Modified epoxy-silver electrodes with palladium nanoparticles. → Simple electroless surface modification. → Wide linear response range. → Easy implementation. - Abstract: A new approach for nonenzymatic glucose sensing, based on a simple modification of epoxy-silver surfaces deposited on the tip of commercial copper electric wires, is presented. Palladium was galvanically displaced on the surface of the epoxy-silver surface in order to obtain metal nanoparticles that act as catalyst for the direct oxidation of glucose. Scanning electron microscopy revealed the formation of the metal nanoparticles. X-ray photoelectron spectroscopy confirmed the metallic nature of the formed nanostructures on the surface. Electrochemical characterization and calibration of the palladium-modified epoxy-silver electrode is reported, obtaining a linear range of 1-20 mM for the detection of glucose with low interference of ascorbic acid and uric acid. A simple 3-step coulometry was used as the detection technique. The developed sensing material is believed to be a great candidate for integration in small devices for clinical essays, due to the simplicity and cost effectiveness of the presented approach, compared to the state-of-the-art devices reported recently in the literature. Simplicity in the coulometry determinations makes these Pd-modified epoxy-silver sensors a good candidate for easy glucose determinations.

German standard methods for the examination of water, waste water and sludge: General measurements of effects and substances (group H), determination of total organic carbon (TOC) (H 3)

International Nuclear Information System (INIS)

1982-01-01

The following method for the determination of the total organic bound carbon is proposed. The carbon of the organic compounds is oxidized to carbon dioxide. There are three oxidation possibilities. Combustion, oxidation with proper oxidation agents in the solution and oxidation by irradiation of ultraviolette light. The resulting carbon dioxide or the possible reduction product methane are analysed with the following measuring instruments: Infrared spectroscopy, acidimetry, coulometry, conductometry, CO 2 sensitive electrodes, heat conductivity detection and flame ionisation detection. (VG) [de

Electrochemical oxidation of zirconium alloys in pre-transition and post-transition kinetic regimes at corrosion in electrolyte solutions

International Nuclear Information System (INIS)

Barkov, A.A.; Shavshin, V.M.

1986-01-01

With the aim of investigation on oxidation of zirconium alloys (Zr+2.5% Nb) the critical thickness of beginning of spalling of froming oxide films in HCl and NHO 3 aqueous solutions was evaluated by coulometry with accelerated procedure. Some variants of predeposition of modificated oxide coatings are proposed increase pre-transition regime time and to decrease corrosion during post-transition regime. Increase in agressivity of solutions (addition of 1 vol.% HF) and UV irradiation are found to increase 3-4 times pre-transition period

Redox chemistry of americium in nitric acid media

Energy Technology Data Exchange (ETDEWEB)

Picart, S.; Jobelin, I.; Armengol, G.; Adnet, JM

2004-07-01

The redox properties of the actinides are very important parameters for speciation studies and spent nuclear fuel reprocessing based on liquid-liquid extraction of actinides at different oxidation states (as in the Purex or Sesame process). They are also very useful for developing analytical tools including coulometry and redox titration. This study addressed the americium(IV)/americium(III) and americium(VI)/americium(V) redox couples, focusing on exhaustive acquisition of the thermodynamic and kinetic parameters of americium oxidation at an electrode in a complexing nitric acid medium. (authors)

Uncertainty propagation for the coulometric measurement of the plutonium concentration in CRM126 solution provided by JAEA

Energy Technology Data Exchange (ETDEWEB)

Morales-Arteaga, Maria [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2017-11-07

This GUM WorkbenchTM propagation of uncertainty is for the coulometric measurement of the plutonium concentration in a Pu standard material (C126) supplied as individual aliquots that were prepared by mass. The C126 solution had been prepared and as aliquoted as standard material. Samples are aliquoted into glass vials and heated to dryness for distribution as dried nitrate. The individual plutonium aliquots were not separated chemically or otherwise purified prior to measurement by coulometry in the F/H Laboratory. Hydrogen peroxide was used for valence adjustment.

Redox chemistry of americium in nitric acid media

International Nuclear Information System (INIS)

Picart, S.; Jobelin, I.; Armengol, G.; Adnet, JM.

2004-01-01

The redox properties of the actinides are very important parameters for speciation studies and spent nuclear fuel reprocessing based on liquid-liquid extraction of actinides at different oxidation states (as in the Purex or Sesame process). They are also very useful for developing analytical tools including coulometry and redox titration. This study addressed the americium(IV)/americium(III) and americium(VI)/americium(V) redox couples, focusing on exhaustive acquisition of the thermodynamic and kinetic parameters of americium oxidation at an electrode in a complexing nitric acid medium. (authors)

Improved laboratory assays of Pu and U for SRP purification and finishing processes

International Nuclear Information System (INIS)

Holland, M.K.; Dorsett, R.S.

1986-01-01

Significant improvements have been made in routine assay techniques for uranium and plutonium as part of an effort to improve accountability at the Savannah River Plant (SRP). Emphasis was placed on input/output accountability points and key physical inventory tanks associated with purification and finishing processes. Improvements were made in existing assay methods; new methods were implemented; and the application of these methods was greatly expanded. Prior to assays, samples were validated via density measurements. Digital density meters precise to four, five, and six decimal places were used to meet specific requirements. Improved plutonium assay techniques are now in routine use: controlled-potential coulometry, ion-exchange coulometry, and Pu(III) diode-array spectrophotometry. A new state-of-the-art coulometer was fabricated and used to ensure maximum accuracy in verifying standards and in measuring plutonium in product streams. The diode-array spectrophotometer for Pu(III) measurements was modified with fiber optics to facilitate remote measurements; rapid, precise measurements made the technique ideally suited for high-throughput assays. For uranium assays, the isotope-dilution mass spectrometric (IDMS) method was converted to a gravimetric basis. The IDMS method and the existing Davies-Gray titration (gravimetric basis) have met accountability requirements for uranium. More recently, a Pu(VI) diode-array spectrophotometric method was used on a test basis to measure plutonium in shielded-cell input accountability samples. In addition, tests to measure uranium via diode-array spectrophotometry were initiated. This rapid, precise method will replace IDMS for certain key sample points

Part I. Application of pulse polarography and pulse anodic stripping to the determination of selected heavy metals in natural waters. Part II. Application of controlled potential coulometric techniques to the determination of uranium

International Nuclear Information System (INIS)

Crosmun, S.T.

1977-06-01

The use of a thin mercury film wax-impregnated graphite electrode for the simultaneous determination of cadmium, lead and zinc in an acetate buffer by differential pulse anodic stripping voltammetry is described. Optimal instrumental parameters for maximum resolution and sensitivity for simultaneous analysis of these three elements in natural waters are discussed. The interference of copper with the determination of zinc is investigated in detail. An optimal mercury film thickness for this electrode is suggested. A method utilizing differential pulse polarography for the determination of chromium (VI) in natural water is described. Additions of 0.62 μg Cu(II) ml -1 and 0.55 μg Fe(III) ml -1 did not interfere with the determination of 0.050 μg Cr(VI) ml -1 . The natural water samples containing Cr(VI) were buffered to approximately pH 7 with 0.1 M ammonium acetate and 0.005 M ethylenediamine and analyzed. Natural water samples of chromium from 0.035 μg to 2.0 μg.ml -1 may be analyzed directly without further preparation. The detection limit is 0.010 μg.ml -1 . A novel, highly efficient cell with integral stirrer for controlled potential coulometry is described. This cell was used to demonstrate the feasibility of determining uranium (VI) by predictive coulometry. A PDP 8/I minicomputer was used to predict the coulometric endpoint with high accuracy within 2.5 minutes in a titration which normally takes about 10 minutes. This technique was shown to yield acceptable results even in the presence of an interfering phosphate matrix

Constant current coulometric method for the determination of uranium in active process solutions

International Nuclear Information System (INIS)

Chitnis, R.T.; Talnikar, S.G.; Paranjape, A.H.

1980-01-01

The determination of uranium in the range of 2.5-5 mg by constant current coulometry is described. The procedure is based on the modified version of the DAVIES - GRAY method, wherein uranium, after the reduction step, is oxidized by adding a known amount of potassium dichromate, and the excess of dichromate is determined by titration with Fe 2+ solution. Fe 2+ ions needed for the titration are generated in situ with 100% current efficiency by electrolytic reduction of Fe 3+ . The method is found to be accurate with a coefficient of variation better than 0.2%. (author)

Determination of Chlorine Dioxide and Chlorite in Water Supply Systems by Verified Methods

Directory of Open Access Journals (Sweden)

Tkáčová Jana

2014-07-01

Full Text Available This work is dedicated to the development and optimization of appropriate analytical methods for the determination of chlorine dioxide and chlorite in drinking water in order to obtain accurate and correct results in the quality control of drinking water. The work deals with the development and optimization of a method for the determination of chlorine dioxide using chlorophenol red. Furthermore, a new spectrophotometric method for the determination of chlorite via bromometry using methyl orange was developed, optimized and validated. An electrochemical method for the determination of chlorite by flow coulometry was also developed, optimized and validated.

Electrochemical Study of Bromide in the Presence of 1,3-Indandione. Application to the Electrochemical Synthesis of Bromo Derivatives of 1,3-Indandione

Directory of Open Access Journals (Sweden)

N. Akaberi

2001-06-01

Full Text Available The electrochemical oxidation of bromide in the presence of 1,3-indandione (1 in water/acetic acid and methanol/acetic acid mixtures has been studied by cyclic voltammetry and controlled-potential coulometry. The results indicate the participation of 1,3-indandione in the bromination reaction. On the basis of the electroanalytical and preparative results a reaction mechanism including electron transfer, chemical reaction and regeneration of bromide was discussed. The electrochemical synthesis of bromo derivatives of 1,3-indandione (2-3 has been successfully performed at constant current, in an undivided cell, in good yield and purity.

Electrochemistry of uranium in sodium chloroaluminate melts

International Nuclear Information System (INIS)

D'olieslager, W.; Meuris, F.; Heerman, L.

1990-01-01

The electrochemical behaviour of uranium was studied in basic, NaCl-saturated NaAlCl 4 melts at 175 deg C. Solutions of UO 3 exhibit two oxidation/reduction waves (cyclic voltammetry). Analysis of the peak currents (cyclic voltammetry), the limiting currents (pulse polarography) and the non-linear log i-t curves (anodic controlled potential coulometry) leads to the conclusion that uranium(IV) in the basic chloroaluminate melt exists as two different species in slow equilibrium with one another, of which only one species can be oxidized to U(VI). (author) 16 refs.; 7 figs.; 3 tabs

Plutonium estimation in the process solutions and oxide dissolved audit samplers by potentiometry using memo titrator

International Nuclear Information System (INIS)

Kumaraguru, K.; Shukla, Y.D.; Vijayan, K.; Ramamoorthy, N.; Jambunathan, U.; Kapoor, S.C.

1990-01-01

Potentiometric method is employed by using memotitrator coupled with combined electrode for the estimation of plutonium. The estimations are carried out on the process samples and the acid dissolved samples for auditing, in the concentration range of 5 g/l to 20 g/l. The chemical procedure is: i)oxidising plutonium to higher oxidation state by silver oxide, ii)reducing the same by adding excess ferrous, and iii)titrating potassium dichromate against the unreacted ferrous. The plutonium content is computed from ferrous consumed in the reaction. The average percentage error of the method is +/-0.27. The values obtained are in close agreement with those obtained by coulometry. (author)

Electrochemical oxidation of 4-morpholinoaniline in aqueous solutions: Synthesis of a new trimer of 4-morpholinoaniline

International Nuclear Information System (INIS)

Esmaili, Roya; Nematollahi, Davood

2011-01-01

Research highlights: → Electrochemical study of 4-morpholinoaniline in various pHs. → Electrochemical trimerization of 4-morpholinoaniline in aqueous solution. → Green method for the synthesis of '4-morpholinoaniline-trimer'. → Potential-pH diagram for 4-morpholinoaniline. - Abstract: Electrochemical oxidation of 4-morpholinoaniline has been studied in various pHs using cyclic voltammetry and controlled-potential coulometry. The electrochemical trimerization of 4-morpholinoaniline is described and its mechanism has been studied in aqueous solution. This method provides a green, reagent-less, and environmentally friendly procedure with high atom economy, for the synthesis of '4-morpholinoaniline-trimer' using a carbon electrode in an undivided cell in good yield and purity.

Electrochemical and spectroscopic studies of tungstencarbonyl complexes containing nitrogen and phosphorous ligands

Directory of Open Access Journals (Sweden)

Haddad Paula S.

2000-01-01

Full Text Available The present work deals with the synthesis, spectroscopic investigation and electrochemical behaviour of the compounds [W(CO4(bipy] (1, [W(CO3(bipy(dppm] (2 and [W(CO3(bipy(dppf] (3, bipy = 2,2'-bipyridine; dppm = bis(diphenylphosphinomethane; dppf = 1,1'-bis(diphenylphosphinoferrocene. The IR and 31P{¹H} NMR spectroscopic data have shown an octahedral coordination geometry for the tungsten atom with the diphosphines acting as monodentate ligands. The electrochemical behaviour of the complexes was investigated by cyclic voltammetry and controlled potential coulometry. Cyclic voltammograms have indicated that the compounds containing diphosphines ligands are more stable towards oxidation than compound (1.

Electrochemistry of chromium subgroup transition metal ions in an ambient temperature chloroaluminate molten salt

International Nuclear Information System (INIS)

Scheffler, T.B.

1984-01-01

The electrochemistry of several chromium subgroup transition metal solutes was studied in the basic AlCl 3 -1-methyl-3-ethylimidazolium chloride (MEIC) ionic liquid at 40.0 0 C by using stationary and rotating disk electrode voltametry, chronoamperometry, coulometry, and UV-vis spectrophotometry. Chromium(III) was present in the melt as the chloro complex [CrCl 6 ] 3- . This complex underwent as essentially irreversible reduction, apparently as a result of slow charge-transfer, to a chromium(II) species at ca. -1.08 V versus an aluminum wire immersed in 66.7 mol % melt. Similar investigations of molybdenum and tungsten were also conducted. Mechanisms are proposed to account for the results

Determination of the oxygen-metal-ratio of uranium-americium mixed oxides

International Nuclear Information System (INIS)

Bartscher, W.

1982-01-01

During the dissolution of uranium-americium mixed oxides in phosphoric acid under nitrogen tetravalent uranium is oxidized by tetravalent americium. The obtained hexavalent uranium is determined by constant potential coulometry. The coulombs measured are equivalent to the oxygen in excess of the minimum composition of UO 2 x AmO 1 . 5 . The total uranium content of the sample is determined in a subsequent coulometric titration. The oxygen-metal ratio of the sample can be calculated for a given uranium-americium ratio. An excess of uranium dioxide is necessary in order to suppress the oxidation of water by tetravalent americium. The standard deviation of the method is 0.0017 O/M units. (orig.) [de

Electrooxidation of 2-propanol compared ethanol on Pd electrode in alkaline medium

Energy Technology Data Exchange (ETDEWEB)

Su, Yuzhi; Xu, Changwei; Liu, Zhaoqing [School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006 (China); Liu, Jianping [Dongguan Entry-exit Inspection and Quarantine Bureau, Dongguan 511700 (China)

2009-10-20

Here, the oxidation activity of 2-propanol compared ethanol on Pd electrode has been studied in alkaline medium. We have used the amount of coulombs (coulometry) and apparent activation energy (E{sub a}) to measure the activity of alcohol electrooxidation. The amount of coulombs during alcohol electrooxidation for 2-propanol is much higher than that of ethanol showing that 2-propanol is more easily electrochemically oxidized than ethanol. The E{sub a} values of 2-propanol are lower than that of ethanol at the potential from -0.45 to -0.375 V which is usually used in direct alcohol fuel cells (DAFCs) indicating that 2-propanol shows better electrooxidation activity than ethanol. (author)

Electrochemical oxidation of 3,5-di-tert-butylcatechol: Synthesis and characterization of the formed ortho-benzoquinhydrone derivative

International Nuclear Information System (INIS)

Nematollahi, D.; Shayani-Jam, H.

2006-01-01

Electrochemical oxidation of 3,5-di-tert-butylcatechol (1) has been studied in ethanol/water mixtures by means of cyclic voltammetry and controlled-potential coulometry. The results revealed that 3,5-di-tert-butyl-1,2-benenzoquinone (2) derived from oxidation of 3,5-di-tert-butylcatechol participate in noncovalently linked interactions with 1 converted to an ortho-benzoquinhydrone (3). The structure of 3 was characterized by MS, IR, 1 H NMR and 13 C NMR. The 1 H NMR studies reveal that the benzoquinhydrone complex 3 is stabilized by one H-bonding interaction. In this work we derived a novel ortho-bezoquinhydrone type complex (3) based on electrochemical oxidation of 3,5-di-tert-butylcatechol at carbon electrode in an undivided cell

Cobalt, titanium or cerium oxide protective coatings for the nickel cathode of the molten carbonate fuel cells; Revetements protecteurs a base d'oxyde de cobalt, de titane ou de cerium pour la cathode de nickel des piles a combustible a carbonates fondus

Energy Technology Data Exchange (ETDEWEB)

Mendoza Blanco, L.

2003-10-15

The aim of this work is to combine the MCFC cathode Li{sub x}Ni{sub 1-x}O properties to those of the protective coatings of LiCoO{sub 2}, Li{sub 2}TiO{sub 3} or of CeO{sub 2}, less soluble in the molten carbonates. In the cases of LiCoO{sub 2}, have been carried out by controlled potential coulometry in aqueous solution, a deposition of Co{sub 3}O{sub 4} on dense Ni. The cobalt oxide reacts rapidly in the Li{sub 2}CO{sub 3}-Na{sub 2}CO{sub 3} medium at 650 C to give LiCoO{sub 2}, a spinel cubic phase revealed by Raman spectroscopy. (O.M.)

Clean and Green Synthesis of New Benzothiazole Derivatives via Electrochemical Oxidation of Catechol Derivatives

Directory of Open Access Journals (Sweden)

Mansour Arab Chamjangali

2016-06-01

Full Text Available Electrochemical oxidation of the catechols 1a and 1b is studied in the presence of 6-methyl-2-thouracil (3b and 6-propyl-2-thiouracil (3a as nucleophiles in a phosphate buffer (0.15 mol L−1, pH = 6.8/DMF (95:5 solution using cyclic voltammetry and controlled-potential coulometry. The results obtained indicate that the quinones derived from the catechols participate in 1,4-Michael-addition reactions with the nucleophiles to form the corresponding new benzothiazole compounds. In this work, we derive a variety of products with good yields using controlled potential at graphite electrodes in an undivided cell. This work is licensed under a Creative Commons Attribution 4.0 International License.

Determination of plutonium and uranium in mixed nuclear fuel by means of potentiostatic and amperostatic coulometry

International Nuclear Information System (INIS)

Kuperman, A.Ya.; Moiseev, I.V.; Galkina, V.N.; Yakushina, G.S.; Nikitskaya, V.N.

1977-01-01

Product solution occurs in HClO 4 + HNO 3 mixing. In prepared plutonium (6) and uranium (6) perchloric acid solution Cl and Cr (6), Mn (7,6,3) foreign oxidizers are selectively reduced with formic and malonic acids. Potentiostatic variant of method is based on successive reduction of Pu(6) to Pu(3) and U(6) to U(4) in 4.5M HCl, containing 5x10 -4 M bismuth (3). In using amperostatic variant of method plutonium and uranium are determined separately. In sulfur-phosphoric acid media plutonium (6) is titrated to Pu(4) with continuously generated iron (2) ions. Uranium (6) in phosphoric acid media is initially reduced to U(4) with Fe(2), and then after Fe(2) excess reduction with nitric acid it is titrated to uranium (6) with continuously electrogenerated manganese (3) ions or vanadium (5). To obtain equivalent point in plutonium (6) and uranium (4) titration amperometric method is used. Coefficient of variation is 0.2-0.3 % rel

SYNTHESIS OF ACETIC ACID FROM ETHANOL BY ELECTROOXIDATION TECHNIQUE USING Ni-Cu-PVC ELECTRODE

Directory of Open Access Journals (Sweden)

Riyanto Riyanto

2017-11-01

Full Text Available A usage of Ni-Cu-PVC electrode for the oxidation of ethanol by electrochemical technique will be reported in this paper. In this work, the effect of electrodes on the yields of acetic acid was determined. Electrode used was made of the mixtures of Ni powder, Cu powder and of polyvinyl chloride (PVC with various percentages. Electrooxidation of 0.20 M ethanol in 0.16 M KOH  (24 mL were carried out using chrono coulometry (CC at a potential of 1050 mV for 6 hours with continious stirring. Electrooxdation result obtained was analyzed using High Performance Liquid Chromatography (HPLC. The test result shows that the composition of  Ni:Cu:PVC  at 75:20:5 have higher efficiency in the electrooxidation of ethanol to acetic acid.

Coulometric titration of niobium in EDTA complexing solution

International Nuclear Information System (INIS)

Pannu, S.S.

1976-01-01

Constant current coulometry of Nb in EDTA was studied employing both potentiometric and amperometric end-point techniques. The titrations were based on the oxidation of Nb(IV)-EDTA with electrogenerated Fe(III) at a graphite anode. The rate of disproportionation of Nb(IV)-EDTA was found to be slow enough not to effect the accuracy sought for the titration. The coulometric titration of Nb in EDTA was found to be more accurate than in 1F sulfuric acid. The mean error in the titrations of 4.76 to 19.65 of Nb in a volume of about 100 ml of 0.02 to 0.04F EDTA was 0.13%. It was found that Ta may be tolerated to a ratio of 1:4, Ta:Nb, in a solution containing 13 mg of Nb. (author)

A study on the electrodeposition of NiFe alloy thin films using chronocoulometry and electrochemical quartz crystal microgravimetry

CERN Document Server

Myung, N S

2001-01-01

Ni, Fe and NiFe alloy thin films were electrodeposited at a polycrystalline Au surface using a range of electrolytes and potentials. Coulometry and EQCM were used for real-time monitoring of electroplating efficiency of the Ni and Fe. The plating efficiency of NiFe alloy thin films was computed with the aid of ICP spectrometry. In general, plating efficiency increased to a steady value with deposition time. Plating efficiency of Fe was lower than that of Ni at -0.85 and -1.0 V but the efficiency approached to the similar plateau value to that of Ni at more negative potentials. The films with higher content of Fe showed different stripping behavior from the ones with higher content of Ni. Finally, compositional data and real-time plating efficiency are presented for films electrodeposited using a range of electrolytes and potentials.

Development of a certified reference material for composition of high-purity copper as a transfer standard within GET 176-2013

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Veniamin M. Zyskin

2017-01-01

Full Text Available Introduction. The paper gives information on the development of a certified reference material (CRM for composition of high-purity copper (Cu CRM UNIIM. The CRM is included as the transfer standard into the State primary standard of the mass (molar fraction and mass (molar concentration of the component in liquid and solid substances and materials based on coulometry GET 176-2013.Materials and methods. The CRM represents pieces of oxygen-free copper wire rod, brand KMB, produced according to GOST R 53803-2010, weighing from 0.5 to 1g. The CRM is packed in plastic vials with the capacity of 30 or 50 cm3. The certified characteristic of the CRM is copper mass fraction in copper wire rod, expressed in percentages. The certified value for copper mass fraction was established by the primary method of controlled-potential coulometry using the State primary standard GET 176-2013.Results. The permitted interval of the certified value for copper mass fraction in the CRM is from 99,950 % to 100,000 %. The relative expanded uncertainty (k=2 of the certified value for copper mass fraction does not exceed 0,030 %; the relative standard uncertainty due to inhomogeneity does not exceed 0.010 %; the relative standard uncertainty due to instability does not exceed 0.010 %. The shelf life of the developed CRM is 10 years provided that standard storage conditions are ensured.Discussion and conclusions. The developed CRM is included into the State register of type approved RMs under the number GSO 10800-2016. The CRM of high-purity copper (Cu CRM UNIIM as a transfer standard is intended for reproduction, storage and transfer of the copper mass fraction unit to other reference materials and chemical reagents by the method of comparison using a comparator and by conducting direct measurements. This CRM may also be used:– for verification of measuring instruments (MIs according to the state verification schedule described in GOST R 8.735.0-2014,– for calibration

Chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium nitrate solutions

International Nuclear Information System (INIS)

Anon.

1981-01-01

These analytical procedures are designed to show whether a given material meets the purchaser's specifications as to plutonium content, effective fissile content, and impurity content. The following procedures are described in detail: plutonium by controlled-potential coulometry; plutonium by amperometric titration with iron(II); free acid by titration in an oxalate solution; free acid by iodate precipitation-potentiometric titration method; uranium by Arsenazo I spectrophotometric method; thorium by thorin spectrophotometric method; iron by 1,10-phenanthroline spectrophotometric method; chloride by thiocyanate spectrophotometric method; fluoride by distillation-spectrophotometric method; sulfate by barium sulfate turbidimetric method; isotopic composition by mass spectrometry; americium-241 by extraction and gamma counting; americium-241 by gamma counting; gamma-emitting fission products, uranium, and thorium by gamma-ray spectroscopy; rare earths by copper spark spectrochemical method; tungsten, niobium (columbium), and tantalum by spectrochemical method; simple preparation by spectrographic analysis for general impurities

Standard test methods for chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade plutonium dioxide powders and pellets

CERN Document Server

American Society for Testing and Materials. Philadelphia

2010-01-01

1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade plutonium dioxide powders and pellets to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Plutonium Sample Handling 8 to 10 Plutonium by Controlled-Potential Coulometry Plutonium by Ceric Sulfate Titration Plutonium by Amperometric Titration with Iron(II) Plutonium by Diode Array Spectrophotometry Nitrogen by Distillation Spectrophotometry Using Nessler Reagent 11 to 18 Carbon (Total) by Direct Combustion–Thermal Conductivity 19 to 30 Total Chlorine and Fluorine by Pyrohydrolysis 31 to 38 Sulfur by Distillation Spectrophotometry 39 to 47 Plutonium Isotopic Analysis by Mass Spectrometry Rare Earth Elements by Spectroscopy 48 to 55 Trace Elements by Carrier–Distillation Spectroscopy 56 to 63 Impurities by ICP-AES Impurity Elements by Spark-Source Mass Spectrography 64 to 70 Moisture by the Coulomet...

Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium nitrate solutions

CERN Document Server

American Society for Testing and Materials. Philadelphia

2010-01-01

1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade plutonium nitrate solutions to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Plutonium by Controlled-Potential Coulometry Plutonium by Amperometric Titration with Iron(II) Plutonium by Diode Array Spectrophotometry Free Acid by Titration in an Oxalate Solution 8 to 15 Free Acid by Iodate Precipitation-Potentiometric Titration Test Method 16 to 22 Uranium by Arsenazo I Spectrophotometric Test Method 23 to 33 Thorium by Thorin Spectrophotometric Test Method 34 to 42 Iron by 1,10-Phenanthroline Spectrophotometric Test Method 43 to 50 Impurities by ICP-AES Chloride by Thiocyanate Spectrophotometric Test Method 51 to 58 Fluoride by Distillation-Spectrophotometric Test Method 59 to 66 Sulfate by Barium Sulfate Turbidimetric Test Method 67 to 74 Isotopic Composition by Mass Spectrom...

Standard test methods for chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade mixed oxides ((U, Pu)O2)

CERN Document Server

American Society for Testing and Materials. Philadelphia

2010-01-01

1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade mixed oxides, (U, Pu)O2, powders and pellets to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Uranium in the Presence of Pu by Potentiometric Titration Plutonium by Controlled-Potential Coulometry Plutonium by Amperometric Titration with Iron (II) Nitrogen by Distillation Spectrophotometry Using Nessler Reagent 7 to 14 Carbon (Total) by Direct Combustion-Thermal Conductivity 15 to 26 Total Chlorine and Fluorine by Pyrohydrolysis 27 to 34 Sulfur by Distillation-Spectrophotometry 35 to 43 Moisture by the Coulometric, Electrolytic Moisture Analyzer 44 to 51 Isotopic Composition by Mass Spectrometry Rare Earths by Copper Spark Spectroscopy 52 to 59 Trace Impurities by Carrier Distillation Spectroscopy 60 to 69 Impurities by Spark-Source Mass Spectrography 70 to 76 Total Gas in Reactor-Grade Mixed Dioxide P...

Uncertainty propagation for the coulometric measurement of the plutonium concentration in MOX-PU4.

Energy Technology Data Exchange (ETDEWEB)

None, None

2017-11-07

This GUM WorkbenchTM propagation of uncertainty is for the coulometric measurement of the plutonium concentration in a Pu standard material (C126) supplied as individual aliquots that were prepared by mass. The C126 solution had been prepared and as aliquoted as standard material. Samples are aliquoted into glass vials and heated to dryness for distribution as dried nitrate. The individual plutonium aliquots were not separated chemically or otherwise purified prior to measurement by coulometry in the F/H Laboratory. Hydrogen peroxide was used for valence adjustment. The Pu assay measurement results were corrected for the interference from trace iron in the solution measured for assay. Aliquot mass measurements were corrected for air buoyancy. The relative atomic mass (atomic weight) of the plutonium from X126 certoficate was used. The isotopic composition was determined by thermal ionization mass spectrometry (TIMS) for comparison but not used in calculations.

Investigation into the dissolution and direct assay of high-fired plutonium dioxide

International Nuclear Information System (INIS)

Patterson, J.K.

1976-01-01

A fusion-melt and dissolution assay method has been developed and tested for the quantitative analysis of high-fired plutonium dioxide. The method employs fusion of the plutonium dioxide at temperatures greater than the melting point of an eutectic mixture of potassium pyrosulfate plus sodium peroxide. The resultant melt is then titrated directly by either controlled potential coulometry or a gravimetric titration, using standardized ceric sulfate as the titrant. It has been concluded from these investigations that by using the techniques described, high-fired plutonium dioxide (stochiometric) can be quantitatively dissolved and assayed to a degree heretofore beyond the state-of-the-art, while showing direct traceability to the Federal standards. After fusion, the dissolution and direct assay is applicable to existing routine analytical procedures. The method was designed so as to minimize physical handling, simplify the chemical operations, and maximize the personal safety of the analyst at an appreciable cost savings per analysis

Use of destructive and nondestructive methods of analysis for quality assurance at MOX fuel production in the Russia

International Nuclear Information System (INIS)

Bibilashvili, Y.K.; Rudenko, V.S.; Chorokhov, N.A.; Korovin, Y.I.; Petrov, A.M.; Vorobiev, A.V.; Mukhortov, N.F.; Smirnov, Y.A.; Kudryavtsev, V.N.

2000-01-01

Parameters of MOX fuel with various plutonium contents are considered from the point of view of necessity of their control for quality assurance. Destructive and nondestructive methods used for this purpose in the Russia are described: controlled potential coulometry for determination of uranium or/and plutonium contents, their ratio and oxygen factor; mass spectrometry for determination of uranium and plutonium isotopic composition; chemical spectral emission method for determination of contents of 'metal' impurities, boron and silicon, and methods of determination of gas forming impurities. Capabilities of nondestructive gamma-ray spectrometry techniques are considered in detail and results of their use at measurement of uranium and plutonium isotopic composition in initial dioxides, at determination of contents of uranium and plutonium, and uniformity of their distribution in MOX powder and pellets. The necessity of correction of algorithm of the MGA program is shown for using the program at analyses of gamma-ray spectra of MOX with low contents of low burnup plutonium. (authors)

Results of the analysis of the intercomparison samples of the depleted uranium dioxide SR-20

International Nuclear Information System (INIS)

Aigner, H.; Deron, S.; Kuhn, E.; Ronesch, K.; Zoigner, A.

Samples of a homogeneous powder of depleted uranium dioxide, SR-20, were distributed to 32 laboratories in January 1980 for intercomparison of the precisions and accuracies of wet chemical assay. 11 laboratories reported their results (ANNEX 1). 5 laboratories applied titration procedures, 4 of them applied methods derived from the Davies and Gray procedure (1), 2 laboratories used controlled potential coulometry, 2 laboratories used precipitation procedures, 1 laboratory used fluorimetry and 1 laboratory used activation analysis. An analysis of variance yields for each laboratory the estimates of the measurement errors, the dissolution or treatment errors and the random calibration errors. The measurement errors vary between 0.01% and 1.7% relative. The differences to the reference value vary between -9.1% and +0.92% uranium, but 9 laboratories agree within +-1%U with the reference value. The mean bias of these 9 laboratories is equal to +0.04%U. The standard deviation of the biases of these 9 laboratories is equal to 0.36%.U

The development of a micropatterned electrode for studies of zinc electrodeposition

Energy Technology Data Exchange (ETDEWEB)

Sutija, Dave P. [Univ. of California, Berkeley, CA (United States); Muller, Rolf H. [Univ. of California, Berkeley, CA (United States); Tobias, Charles W. [Univ. of California, Berkeley, CA (United States)

1986-12-01

A micropatterned electrode was prepared for the study of electrocrystallization. Using microphotolithography, in conjunction with evaporation and pulse electrodeposition of thin films, a set of artificially roughened electrodes with hemispherical surface features five microns in diameter was developed. Voltammetric studies were conducted to determine the best electrode material. Gold, platinum, and various carbon surfaces were evaluated for zinc nucleation density and hydrogen overpotential. Surface homogeneity was examined by both light and scanning electron microscopy. Gold was determined to possess the best combination of material properties: chemical inertness, low melting point, and a high work function allowing underpotential deposition of zinc which reduces the rate of hydrogen evolution. Stripping coulometry was employed to determine zinc limiting currents, and evaluate effective diffusion coefficients in concentrated zinc chloride solutions. Although the method worked well for dilute zinc chloride and copper sulfate solutions, it failed at higher current densities; the emergence of surface roughness obscured actual limiting current plateaus.

Purity Assessment of Organic Reference Materials with a Mass Balance Method: A Case Study of Endosulfan-II

International Nuclear Information System (INIS)

Kim, Seunghyun; Lee, Joonhee; Ahn, Seonghee; Song, Youngsin; Kim, Dongkyun; Kim, Byungjoo

2013-01-01

A mass balance method established in this laboratory was applied to determine the purity of an endosulfan-II pure substance. Gas chromatography-flame ionization detector (GC-FID) was used to measure organic impurities. Total of 10 structurally related organic impurities were detected by GC-FID in the material. Water content was determined to be 0.187% by Karl-Fischer (K-F) coulometry with an oven-drying method. Nonvolatile residual impurities was not detected by Thermal gravimetric analysis (TGA) within the detection limit of 0.04% (0.7 μg in absolute amount). Residual solvents within the substance were determined to be 0.007% in the Endosulfan-II pure substance by running GC-FID after dissolving it with two solvents. The purity of the endosulfan-II was finally assigned to be (99.17 ± 0.14)%. Details of the mass balance method including interpretation and evaluating uncertainties of results from each individual methods and the finally assayed purity were also described

Synthesis, electrochemical, spectrophotometric and potentiometric studies of two azo-compounds derived from 4-amino-2-methylquinoline in ethanolic-aqueous buffered solutions

Energy Technology Data Exchange (ETDEWEB)

El-Attar, Mona A.; Ghoneim, Mohamed M. [Analytical Chemistry Research Unit, Chemistry Department, Tanta University (Egypt); Ismail, Iqbal M., E-mail: maema.2011@yahoo.com [Chemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah (Saudi Arabia)

2012-08-15

Two azo-compounds, 2-methyl-4-(5-amino-2-hydroxy-phenylazo)-quinoline (2) and 2-methyl-4-(2-hydroxy-5-nitrophenylazo)-quinoline, derived from 4-amino-2-methylquinoline were synthesized. Their chemical structures were characterized and confirmed by means of elemental chemical analysis, infrared (IR) spectroscopy, {sup 1}H nuclear magnetic resonance (NMR) and mass spectrometry (MS). The electrochemical behavior of the starting compound (4-amino-2-methylquinoline) and of the two synthesized azo-derivatives was studied at the mercury electrode in the B-R universal buffer at various pH values (2-11.5) containing 40% (v/v) ethanol using dc-polarography, cyclic voltammetry and controlled-potential coulometry. Their electrode reaction pathways were elucidated and discussed. The dissociation constants (pKa) of the examined compounds, stability constants and stoichiometry of their complexes in solution with some transition metal ions (Co(II), Ni(II), Cu(II), La(III) and UO{sup 2+}{sub 2}) were determined. (author)

Results of the analysis of the intercomparison samples of the depleted uranium dioxide SR-10

International Nuclear Information System (INIS)

Aigner, H.; Deron, S.; Kuhn, E.; Zoigner, A.

1981-01-01

Samples of a homogeneous powder of depleted uranium dioxide, SR-10, were distributed to 27 laboratories in February 1979 for intercomparison of the precisions and accuracies of wet chemical assay. 7 laboratories reported their results. 6 laboratories applied titration procedures, 4 of them applied methods derived from the Davies and Gray procedure (1), and one laboratory used controlled potential coulometry. An analysis of variance yields for each laboratory the estimates of the measurement errors, the dissolution or treatment errors and the random calibration errors. The measurement errors vary between 0.01% and 0.10% relative. The differences to the reference value vary between -0.48% and +0.87% uranium, but 5 laboratories agree within +-0.25% U with the reference value. The biases of 5 laboratories are greater than expected from their random errors. The mean bias of the 7 laboratories is equal to +0.03% U. The standard deviation of the laboratory biases is equal to 0.43% U. (author)

Oxidative coupling and polymerization of pyrroles

International Nuclear Information System (INIS)

Hansen, Gregers Hendrik; Henriksen, Rikke Morck; Kamounah, Fadhil S.; Lund, Torben; Hammerich, Ole

2005-01-01

The electrochemical oxidation of 2,4-dimethyl-3-ethylpyrrole in acetonitrile has been studied using cyclic voltammetry, constant current coulometry, preparative electrolyses and ab initio calculations. The product analysis after the preparative electrolyses was carried out by HPLC combined with UV-vis and electrospray ionization MS detection. The aim of the work was to address some of the unresolved problems in the oxidative oligomerization and polymerization of alkylpyrroles. The title compound was chosen as a model for studies of pyrroles that are more basic than the solvent-supporting electrolyte system and for that reason are forced to serve as the base accepting the protons released during the coupling steps. The voltammograms obtained by cyclic voltammetry at a substrate concentration of 2 mM and voltage scan rates between 0.02 and 2 V s -1 showed a characteristic trace-crossing phenomenon that could be demonstrated by digital simulation to be related to that fact that the deprotonations of the initially formed dimer dication are slow with second order rate constants in the range 10 3 -10 4 M -1 s -1 . The relative stability of the different tautomers of the protonated pyrrole monomer and the corresponding 2,2'-dimer was determined by ab initio calculations at the RHF 6-31G(d) level. The studies also included investigations of the effects resulting from addition of a non-nucleophilic base, 2,6-di-tert-butylpyridine, to the voltammetry solutions. The major product observed after preparative electrolyses was a trimer the structure of which is proposed to include a central 2H-pyrrole unit. Since 2H-pyrroles are stronger bases than the corresponding 1H-pyrroles, the trimer is effectively protected against further oxidation by protonation. Two other trimers were observed as minor or trace products as well as a 1H,2H-dimer and several tetramers, also in trace amounts. In addition to the dimer, the trimers and the tetramers, a number of other minor products could be

Electrosynthesis of Clozapine Drug Derivative via an EC Electrochemical Mechanism

Directory of Open Access Journals (Sweden)

Esmail Tammari

2017-12-01

Full Text Available The fact that oxidation, as one of the main routes of phase I metabolism of drugs, follows by conjugation reactions, and also formation of nitrenium ion as one of the clozapine oxidation products, directed us to investigate the oxidation of clozapine (CLZ in the presence of nucleophile. The oxidation of clozapine (CLZ has been studied on a glassy carbon electrode in the absence and presence of 2-thiobarbituric acid (TBA as nucleophile in aqueous medium by means of cyclic voltammetry and on the graphite rods in controlled-potential coulometry. Cyclic voltammetry studies were realized for CLZ in the pHs 1.0 to 8.0. Results indicate that the electrochemical behavior of CLZ depends on the pH. Based on the obtained electrochemical results, an ECE mechanism was proposed to explain the electrochemical oxidation of CLZ. The results revealed that oxidized CLZ participates in Michael type addition reaction with TBA and via an EC mechanism converts to the corresponding new dibenzodiazepin derivatives. The product has been characterized by IR, 1H NMR, 13C NMR and MS.

Novel Calibration Technique for a Coulometric Evolved Vapor Analyzer for Measuring Water Content of Materials

Science.gov (United States)

Bell, S. A.; Miao, P.; Carroll, P. A.

2018-04-01

Evolved vapor coulometry is a measurement technique that selectively detects water and is used to measure water content of materials. The basis of the measurement is the quantitative electrolysis of evaporated water entrained in a carrier gas stream. Although this measurement has a fundamental principle—based on Faraday's law which directly relates electrolysis current to amount of substance electrolyzed—in practice it requires calibration. Commonly, reference materials of known water content are used, but the variety of these is limited, and they are not always available for suitable values, materials, with SI traceability, or with well-characterized uncertainty. In this paper, we report development of an alternative calibration approach using as a reference the water content of humid gas of defined dew point traceable to the SI via national humidity standards. The increased information available through this new type of calibration reveals a variation of the instrument performance across its range not visible using the conventional approach. The significance of this is discussed along with details of the calibration technique, example results, and an uncertainty evaluation.

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

Directory of Open Access Journals (Sweden)

Milan Zimpl

2012-01-01

Full Text Available Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds.

Electrochemical behavior of quinoxalin-2-one derivatives at mercury electrodes and its analytical use.

Science.gov (United States)

Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

2012-01-01

Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds.

Modern Directions for Potentiometric Sensors

Science.gov (United States)

Bakker, Eric; Chumbimuni-Torres, Karin

2009-01-01

This paper gives an overview of the newest developments of polymeric membrane ion-selective electrodes. A short essence of the underlying theory is given, emphasizing how the electromotive force may be used to assess binding constants of the ionophore, and how the selectivity and detection limit are related to the underlying membrane processes. The recent developments in lowering the detection limits of ISEs are described, including recent approaches of developing all solid state ISEs, and breakthroughs in detecting ultra-small quantities of ions at low concentrations. These developments have paved the way to use potentiometric sensors as in ultra-sensitive affinity bioanalysis in conjunction with nanoparticle labels. Recent results establish that potentiometry compares favorably to electrochemical stripping analysis. Other new developments with ion-selective electrodes are also described, including the concept of backside calibration potentiometry, controlled current coulometry, pulsed chronopotentiometry, and localized flash titration with ion-selective membranes to design sensors for the direct detection of total acidity without net sample perturbation. These developments have further opened the field for exciting new possibilities and applications. PMID:19890473

Standard test method for determining plutonium by controlled-potential coulometry in H2SO4 at a platinum working electrode

CERN Document Server

American Society for Testing and Materials. Philadelphia

1990-01-01

1.1 This test method covers the determination of milligram quantities of plutonium in unirradiated uranium-plutonium mixed oxide having a U/Pu ratio range of 0.1 to 10. This test method is also applicable to plutonium metal, plutonium oxide, uranium-plutonium mixed carbide, various plutonium compounds including fluoride and chloride salts, and plutonium solutions. 1.2 The recommended amount of plutonium for each aliquant in the coulometric analysis is 5 to 10 mg. Precision worsens for lower amounts of plutonium, and elapsed time of electrolysis becomes impractical for higher amounts of plutonium. 1.3 The values stated in SI units are to be regarded as standard. No other units are to be regarded as standard. 1.4 This standard does not purport to address all of the safety concens, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific precaution...

Results of the analyses of the intercomparison samples of natural dioxide SR-1

International Nuclear Information System (INIS)

Aigner, H.; Kuhn, E.; Deron, S.

1980-08-01

Samples of a homogeneous powder of natural uranium dioxide, SR-1, were distributed to 37 laboratories in November 1977 for intercomparison of the precisions and accuracies of wet chemical assays. 17 laboratories reported 18 sets of results (one laboratory applied two techniques). The analytical methods which were applied were: titration (11), coulometry (2), precipitation-gravimetry (1), flourimetry (2), X-Ray flourescence (1) and neutron activation (1). Analysis of variance yield for each combination of laboratory and technique the estimates of the measurement errors, the dissolution or treatment errors and the fluctuation of the measurements between sample bottles. Time effects have also been tested. The measurement errors vary between 0.01% and 6.4%. Eleven laboratories agree within 0.25% with the reference value. No mean obtained by wet chemical methods is biased by more than 0.4%. The biases of the other methods (flourimetry, X-Ray fluorescence and neutron activation) vary between 0.5% and 4.3%. The biases of 9 laboratories or techniques are greater than expected from their random errors. The mean bias of the fourteen wet chemical methods is equal to 0.08% U with a standard deviation of +-0.18% U

Elemental and organic carbon in flue gas particles of various wood combustion systems

Energy Technology Data Exchange (ETDEWEB)

Gaegauf, C.; Schmid, M.; Guentert, P.

2005-12-15

The airborne particulate matter (PM) in the environment is of ever increasing concern to authorities and the public. The major fractions of particles in wood combustion processes are in the size less than 1 micron, typically in the range of 30 to 300 nm. Of specific interest is the content of the elemental carbon (EC) and organic carbon (OC) in the particles since these substances are known for its particular potential as carcinogens. Various wood combustion systems have been analysed (wood chip boiler, pellet boiler, wood log boiler, wood stove and open fire). The sampling of the particles was done by mean of a multi-stage particle sizing sampler cascade impactor. The impactor classifies the particles collected according to their size. The 7 stages classify the particles between 0.4 and 9 microns aerodynamic diameter. The analytical method for determining the content of EC and OC in the particles is based on coulometry. The coulometer measures the conductivity of CO{sub 2} released by oxidation of EC in the samples at 650 {sup o}C. The OC content is determined by pyrolysis of the particle samples in helium atmosphere.

Environmental pollution

International Nuclear Information System (INIS)

Hanif, J.; Hanif, M.I.

1997-01-01

The third proceedings of National Symposium on Modern Trends in Contemporary Chemistry was held in Islamabad, Pakistan from February 24-26, 1997. In this symposium more than 220 scientists, engineers and technologist were registered from 11 universities, 17 research organisations and 8 non-governmental organisation including some commercial establishments. The symposium was divided into five technical sessions on hydro spheric pollution, atmospheric pollution, bio spheric pollution, lithospheric pollution and impact assessment and environmental education. Environmental and ecology are so interdependent that any change in the balance due to natural and man made cause may result in a disaster, flood, fire, earthquake, epidemic, population explosion etc. are the natural ways of unbalancing our ecosystem. The scope of this symposium includes: 1) Review the chemistry and the chemical techniques like polarography, coulometry, HPLC, GC-MS, NAA, XRF, AAS, AES etc. involved in the assessment monitoring and control of various pollutions. 2) Propose sampling, transportation, measurement and standardization procedures. 3) Collaboration in scientific data collection. 4) Mutual consultation for management of the pollution problem in a cost effective manner. 5) sharing knowledge and experience with various environmental protection groups both in public and private sector. (A.B.)

A new approach to flow-batch titration. A monosegmented flow titrator with coulometric reagent generation and potentiometric or biamperometric detection.

Science.gov (United States)

de Aquino, Emerson Vidal; Rohwedder, Jarbas José Rodrigues; Pasquini, Celio

2006-11-01

Monosegmented flow analysis (MSFA) has been used as a flow-batch system to produce a simple, robust, and mechanized titrator that enables true titrations to be performed without the use of standards. This paper also introduces the use of coulometry with monosegmented titration by proposing a versatile flow cell. Coulometric generation of the titrand is attractive for titrations performed in monosegmented systems, because the reagent can be added without increasing the volume of sample injected. Also, biamperomeric and potentiometric detection of titration end-points can increase the versatility of the monosegmented titrator. The cell integrates coulometric generation of the titrand with detection of end-point by potentiometry or biamperometry. The resulting titrator is a flow-batch system in which the liquid monosegment, constrained by the interfaces of the gaseous carrier stream, plays the role of a sample of known volume to be titrated. The system has been used for determination of ascorbic acid, by coulometric generation of I2 with biamperometric detection, and for determination of Fe(II), by coulometric generation of Ce(IV) with potentiometric detection of the end-point, both in feed supplements.

Standard method of test for atom percent fission in uranium fuel - radiochemical method

International Nuclear Information System (INIS)

Anon.

The determination of the U at. % fission that has occurred in U fuel from an analysis of the 137 Cs ratio to U ratio after irradiation is described. The method is applicable to high-density, clad U fuels (metal, alloys, or ceramic compounds) in which no separation of U and Cs has occurred. The fuels are best aged for several months after irradiation in order to reduce the 13-day 136 Cs activity. The fuel is dissolved and diluted to produce a solution containing a final concentration of U of 100 to 1000 mg U/l. The 137 Cs concentration is determined by ASTM method E 320, for Radiochemical Determination of Cesium-137 in Nuclear Fuel Solutions, and the U concentration is determined by ASTM method E 267, for Determination of Uranium and Plutonium Concentrations and Isotopic Abundances, ASTM method E 318, for Colorimetric Determination of Uranium by Controlled-Potential Coulometry. Calculations are given for correcting the 137 Cs concentration for decay during and after irradiation. The accuracy of this method is limited, not only by the experimental errors with which the fission yield and the half-life of 137 Cs are known

Automated sample-processing and titration system for determining uranium in nuclear materials

International Nuclear Information System (INIS)

Harrar, J.E.; Boyle, W.G.; Breshears, J.D.; Pomernacki, C.L.; Brand, H.R.; Kray, A.M.; Sherry, R.J.; Pastrone, J.A.

1977-01-01

The system is designed for accurate, precise, and selective determination of from 10 to 180 mg of uranium in 2 to 12 cm 3 of solution. Samples, standards, and their solutions are handled on a weight basis. These weights, together with their appropriate identification numbers, are stored in computer memory and are used automatically in the assay calculations after each titration. The measurement technique (controlled-current coulometry) is based on the Davies-Gray and New Brunswick Laboratory method, in which U(VI) is reduced to U(IV) in strong H 3 PO 4 , followed by titration of the U(IV) with electrogenerated V(V). Solution pretreatment and titration are automatic. The analyzer is able to process 44 samples per loading of the sample changer, at a rate of 4 to 9 samples per hour. The system includes a comprehensive fault-monitoring system that detects analytical errors, guards against abnormal conditions which might cause errors, and prevents unsafe operation. A detailed description of the system, information on the reliability of the component subsystems, and a summary of its evaluation by the New Brunswick Laboratory are presented

Polarographic studies about indium (III) behaviour in aqueous media of sodium azide

International Nuclear Information System (INIS)

Tokoro, R.

1988-01-01

The present study shows some polarographic behavior of indium (III) in azide media that is close those observed in a thiocyanate solution. The presence of azide ligand decreases the overpotential in the discharge of indium whose catalytic character can be explained by formation of an azide bridge between electrode and indium (III) increasing the speed of electron transfer. The discharge of indium in azide media is diffusion controlled. As the azide concentration is increased the half wave potential displaces in the cathodic direction. This displacement is due to complex formation. The number of electrons, n, involved in the total process was estimates by the reversible polarographic equation to be 2,7. The potentiostatic coulometry of indium in azide/hydrazoic acid buffer showed a catalytic process where the chemistry regeneration was performed by reaction of hydrazoic acid and indium amalgam. The electrochemistry evidence was the constancy of current as the electrolysis proceeded. The chemistry aspect was the presence of ammonium cation in electrolysed solution. The catalytic process with chemistry regeneration and the formation of a bridge by azide could explain the higher value of current in azide media compared to perchlorate solution. (author) [pt

Preparation of carbonaceous electrodes and evaluation of their performance by electrochemical techniques

International Nuclear Information System (INIS)

Sharma, H.S.; Manolkar, R.B.; Kamat, J.V.; Marathe, S.G.; Biswas, A.R.; Kulkarni, P.G.

1994-01-01

Carbonaceous electrodes, from glassy carbon (GC), graphite rod or graphite powder, have been prepared for coulometric and voltammetric investigation. Beaker type graphite electrode of larger surface area was used as working electrode for the analysis of uranium and plutonium in solution by coulometry. Results have shown usefulness of the electrode for both uranium and plutonium analysis. Thus the graphite electrode can be used in place of mercury for uranium analysis and in place of platinum gauze for plutonium analysis. GC electrode ( from French and Indian material ), graphite or carbon paste electrode of smaller surface area prepared here have also been found to give satisfactory performance as could be observed from cyclic voltammetric (cv) patterns for standard K 9 Fe(CN) 6 /K 4 Fe(CN) 6 redox system. Especially the GC electrode, (French) polished to 1μ finish with diamond paste gave very low values (1μ amp.) of background current in 1M KCl and the difference in cathodic and anodic peak potentials (δE values) was close to 60 mV from one electron transfer. Therefore the electrode can be used for various types of electrochemical studies relating to redox potentials, reaction mechanism, kinetic parameters etc. of different electrode processes. (author). 20 refs., 3 tabs., 10 figs., 8 photographs

Reference materials and interlaboratory comparison for actinide analysis

International Nuclear Information System (INIS)

Hanssens, Alain; Viallesoubranne, Carole; Roche, Claude; Liozon, Gerard

2008-01-01

Measurement quality is crucial for the safety of nuclear facilities and is a primary requirement for fissile material monitoring and accountancy. CETAMA (Cea Committee for the establishment of analysis methods), in collaboration with Cea and AREVA laboratories, fabricates certified reference materials and organizes interlaboratory comparison programs for plutonium and uranium assay in solution. A new plutonium metal measurement standard (MP3) is currently being prepared by Cea and is a subject of cooperative work in view of its certification and use by analysis laboratories. U and Pu interlaboratory comparisons are carried out at regular intervals on benchmark samples in coordination with working groups from French nuclear laboratories. These programs are supported by international cooperation. 'Chemical' methods (potentiometry, gravimetric analysis, etc.) generally provide the best accuracy. Coulometry is the benchmark technique for plutonium assay: its metrological qualities should be an incentive for wider use by laboratories performing precise control assays of plutonium as well as uranium. Gravimetric analysis provides excellent results for analysis of pure uranyl nitrate solutions. In view of its many advantages we encourage laboratories to employ this technique to assay pure U or Pu solutions. 'Physical' or 'physicochemical' methods are increasingly used, and their performance has improved. K-edge absorption spectrometry and isotope dilution mass spectrometry are capable of reaching measurement quality levels comparable to those of the best 'chemical' methods. (authors)

Progress report, Chemistry and Materials Division, 1 October - 31 December, 1980

International Nuclear Information System (INIS)

1981-02-01

Experiments with aluminum-indium single crystals in which the indium atoms occupy interstitial positions have enabled the first direct measurements of ion flux gradients to be made for a particular channel. A search is being carried out for tri-, tetra-, and hexa-vacancy clusters centered on interstitial indium or tin atoms in irradiated copper single crystal alloys. Work on hydrogen and helium ion scattering at keV energies from tungsten and tungsten oxide. Research is being carried out on dithiothreitol in aqueous solution with nitrate ion to improve understanding of the radiation chemistry of sulphydryl compounds. A short pulse carbon dioxide laser is being used in experiments on the multiphoton absorption and decomposition of alcohols. The separation factor for isotope exchange between heavy water and hydrogen gas has been measured as a function of temperature from 5 to 95 0 C. A procedure has been developed for the determination of gadolinium, samarium, europium and dysprosium at levels down to 10 -7 g.g -1 in ThO 2 by emission spectroscopy. It is now possible to determine uranium with high precision and accuracy in 2 percent uranium-thorium dioxide fuel by controlled potential coulometry. It has been shown that cracking of Zr-2.5 percent Nb in hydrogen gas is not pressure-dependent. The solubility of tin in zirconium has been studied. (L.L.)

Study of the degradation of the insulation of HV cables with PVC insulation

International Nuclear Information System (INIS)

Quennehen, Pierre

2014-01-01

The observed decrease in the resistivity of the PVC insulation of some high voltage unipolar cables led to question their ability to perform their function. Provide answers concerning in particular the origin of the variation in resistivity and the impact on the dielectric strength were the objectives of this study. The characterizations were carried on cables withdrawn from service whose properties had changed during their use. Physico-chemical characterization (IR microscopy, UV spectroscopy, SEM - EDX and coulometry) showed that aging of the cable resulted from a mechanism of dehydro-chlorination. The presence of two modes of electric conduction in the material was observed: electronic conduction at a low temperature (≤ -10 C) and ionic conduction at room temperature and beyond. The presence of these two modes of conduction is consistent with the mechanism of dehydro-chlorination. In contrast to an Arrhenius law, artificial aging showed a threshold effect in the thermal activation of the mechanism at the origin of the resistivity drop. The dielectric strength of the cable has been confirmed by tests at voltages or temperatures well beyond the nominal values. Measurements of differential scanning calorimetry (DSC) showed occasional more or less pronounced over-heatings that correlate with the resistivity drops, and can therefore be considered as being at the origin of the observed evolutions. (author)

Electrochemical Study of Iodide in the Presence of Phenol and o-Cresol: Application to the Catalytic Determination of Phenol and o-Cresol

Directory of Open Access Journals (Sweden)

Davood Nematollahi

2004-11-01

Full Text Available Abstract: The electrochemical oxidation of iodide in the presence of phenol and o-cresol was investigated at a glassy carbon electrode in buffered media by cyclic voltammetry, linear sweep voltammetry and controlled–potential coulometry. The experimental results indicate that the phenol and o-cresol convert to their derivatives after participating in a halogenation coupled reaction (quasi-catalytic reaction following the oxidation of iodide to iodine. The concentrations of phenol and o-cresol have been determined in aqueous solutions according to the linear dependence of quasi-catalytic peak currents with the concentration. The calibration graphs show two linear sections of 0.0 to 1.0×10-4 M and 2.0×10-4 to 1.0 ×10-3 M for phenol and 4.2×10-5 to 1.0×10-4 M and 2.0×10-4 to 1.0×10-3 M for o-cresol. The theoretical detection limits and the relative standard deviations for ten measurements of phenol and o-cresol are 1.125×10-5 M, 1.06% and 4.201×10-5 M, 1.44%, respectively.

Nuclear material safeguards surveillance and accountancy by isotope correlation techniques

International Nuclear Information System (INIS)

Persiani, P.J.; Goleb, J.A.

1981-01-01

This paper presents the initial phase of the US study program and involves the computation of isotopic correlations for the LMFBR fuel cycle. The LWR fuel cycle phase of the study is currently in progress. The selection of the more safeguards effective functionals will depend not only on the level of reliability of isotope correlation technique (ICT) for verification, but also on the capability and difficulty of developing measurement methods. Performance characteristics of existing and proposed isotopic measurement techniques cover the general areas including assay and isotopic wet chemistry and NDA: (1) simultaneous multicomponent analysis techniques, (2) mass spectrometry, (3) x-ray fluorescence or densitometry with high flux monochromatic x-ray sources and high dispersion spectrometers, (4) passive and active neutron interrogation, (5) high level gamma-ray spectroscopy, (6) coulometry, and (7) potentiometry. The measurement capabilities and inherent limitations of these systems are to be evaluated in terms of total systems, operational mode, sample preparation requirements and consequent effect on dissolver solution representation, accuracy and precision estimates (if available), development status of the technique, and development requirements. The isotopic correlation technique shows considerable promise for use in verifying the initial isotopic composition and burnup of discharged assemblies based on the measured ratios of several key isotopes, obtained probably at the dissolver stage in reprocessing. This technique should, for example, easily be capable of indicating the exchange of a blanket assembly for a fuel assembly

Electrooxidation of borohydride on platinum and gold electrodes: implications for direct borohydride fuel cells

International Nuclear Information System (INIS)

Gyenge, Elod

2004-01-01

The electrochemical oxidation of BH 4 - in 2 M NaOH on Pt and Au (i.e. catalytic and non-catalytic electrodes, respectively, for BH 4 - hydrolysis accompanied by H 2 evolution) has been studied by cyclic voltammetry, chrono-techniques (i.e., potentiometry, amperometry, coulometry) and electrochemical impedance spectroscopy. In the case of Pt the cyclic voltammetry behaviour of BH 4 - is influenced by both, the catalytic hydrolysis of BH 4 - yielding H 2 (followed by electrooxidation of the latter at peak potentials between -0.7 and -0.9 V versus Ag/AgCl, KCl std ) and direct oxidation of BH 4 - at more positive potentials, i.e., between -0.15 and -0.05 V. Thiourea (TU, 1.5x10 -3 M) was an effective inhibitor of the catalytic hydrolysis associated with BH 4 - electrooxidation on Pt. Therefore, in the presence of TU, only the direct oxidation of BH 4 - has been detected, with peak potentials between -0.2 and 0 V. It is proposed that TU could improve the BH 4 - utilization efficiency and the coulombic efficiency of direct borohydride fuel cells using catalytic anodes. The electrooxidation of BH 4 - on Pt/TU is an overall four-electron process, instead of the maximum eight electrons reported for Au, and it is affected by adsorbed species such as BH 4 - (fractional surface coverage ∼0.3), TU and possibly reaction intermediates

Electrochemical studies of quinine in surfactant media using hanging mercury drop electrode: a cyclic voltammetric study.

Science.gov (United States)

Dar, Riyaz Ahmad; Brahman, Pradeep Kumar; Tiwari, Sweety; Pitre, Krishna Sadashiv

2012-10-01

The electrochemical behavior of quinine was investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV) using surfactant. The reduction peak current of quinine increases remarkably in presence of 1% CTAB. Its electrochemical behavior is quasi-reversible in the Britton-Robinson buffers of pH 10.38 by exhibiting the well-defined single cathodic and anodic waves and the ratio of I(p)(a)/I(p)(c) approaching one at the scan rate of 500 mVs(-1). On the basis of CV, SWV and Coulometry, electrochemical reduction mechanism of quinine has been proposed which has shown that protonation occurs on the nitrogen of the quinoline moiety. Linearity was obtained when the peak currents (I(p)) were plotted against concentrations of quinine in the range of 30.0-230.0 ng mL(-1) with a detection limit of 0.132 ng mL(-1) in SWV and 90.0-630.0 ng mL(-1) with a detection limit of 0.238 ng mL(-1) in DPV. Fast and sensitive SWV has been applied for the quantitative analysis of quinine in bark of Cinchona sp. and in soft drinks and a good recovery was obtained. The accuracy and precision of the method are determined and validated statistically. No interferences from other food additives were observed. The relative standard deviation for intraday and interday assay was 0.89 and 0.73% (n=3) respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

On-line monitoring of low-level plutonium concentrations

International Nuclear Information System (INIS)

Hofstetter, K.J.; Huff, G.A.; Rebagay, T.V.

1979-10-01

An on-line monitor has been developed to assay plutonium in nitric acid solutions. The performance of the monitor has been assessed by a laboratory experimentation program using solutions with plutonium concentrations from 0.1 to 10 g/l. These conditions are typical of the plutonium solutions in an input stream to a plutonium-purification cycle in a reprocessing plant following uranium/plutonium partitioning. The monitoring system can be fully automated and shows great promise for detecting and quantifying plutonium in situ, thus minimizing the reliance on traditional sampling and laboratory-analysis techniques. The total concentration and isotopic abundance of plutonium are determined by measuring the absolute intensities of the low-energy gamma rays characteristics of 238 Pu, 239 Pu, and 240 Pu nuclides by direct gamma-ray spectroscopy and computer analysis of the spectral data. The addition of a monitoring system of this type to the input stream of a plutonium-purification cycle along with other suitable monitors on the waste streams and on the product stream provides the basis for a near real-time materials control and inventory system. Results of the laboratory-evaluation program employing plutonium in solutions with isotopic compositions typical of those involved in processing light water reactor fuels are presented. The detailed design of a monitoring cell and detection system is given. The precision and accuracy of the results relative to those measured by mass spectrometry and controlled potential coulometry are also summarized

Comparation of fundamental analytical methods for quantitative determination of copper(IIion

Directory of Open Access Journals (Sweden)

Ačanski Marijana M.

2008-01-01

Full Text Available Copper is a ductile metal with excellent electrical conductivity, and finds extensive use as an electrical conductor, heat conductor, as a building material, and as a component of various alloys. In this work accuracy of methods for quantitative determination (gravimetric and titrimetric methods of analysis of copper(II ion was studied. Gravimetric methods do not require a calibration or standardization step (as all other analytical procedures except coulometry do because the results are calculated directly from the experimental data and molar masses. Thus, when only one or two samples are to be analyzed, a gravimetric procedure may be the method of choice because it involves less time and effort than a procedure that requires preparation of standards and calibration. In this work in gravimetric analysis the concentration of copper(II ion is established through the measurement of a mass of CuSCN and CuO. Titrimetric methods is a process in which a standard reagent is added to a solution of an analyze until the reaction between the analyze and reagent is judged to be complete. In this work in titrimetric analysis the concentration of copper(II ion is established through the measurement of a volume of different standard reagents: Km, Na2S2O3 and AgNO3. Results were discussed individually and mutually with the aspect of exactility, reproductivity and rapidity. Relative error was calculated for all methods.

Hierarchical Porous Carbon Spheres for High-Performance Na-O2 Batteries.

Science.gov (United States)

Sun, Bing; Kretschmer, Katja; Xie, Xiuqiang; Munroe, Paul; Peng, Zhangquan; Wang, Guoxiu

2017-12-01

As a new family member of room-temperature aprotic metal-O 2 batteries, Na-O 2 batteries, are attracting growing attention because of their relatively high theoretical specific energy and particularly their uncompromised round-trip efficiency. Here, a hierarchical porous carbon sphere (PCS) electrode that has outstanding properties to realize Na-O 2 batteries with excellent electrochemical performances is reported. The controlled porosity of the PCS electrode, with macropores formed between PCSs and nanopores inside each PCS, enables effective formation/decomposition of NaO 2 by facilitating the electrolyte impregnation and oxygen diffusion to the inner part of the oxygen electrode. In addition, the discharge product of NaO 2 is deposited on the surface of individual PCSs with an unusual conformal film-like morphology, which can be more easily decomposed than the commonly observed microsized NaO 2 cubes in Na-O 2 batteries. A combination of coulometry, X-ray diffraction, and in situ differential electrochemical mass spectrometry provides compelling evidence that the operation of the PCS-based Na-O 2 battery is underpinned by the formation and decomposition of NaO 2 . This work demonstrates that employing nanostructured carbon materials to control the porosity, pore-size distribution of the oxygen electrodes, and the morphology of the discharged NaO 2 is a promising strategy to develop high-performance Na-O 2 batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic Reference Electrode development for redox potential measurements in fluoride molten salt at high temperature

International Nuclear Information System (INIS)

Durán-Klie, Gabriela; Rodrigues, Davide; Delpech, Sylvie

2016-01-01

Measurement of redox potential in fluoride media is a major problem due to the difficulty to design a reference electrode with high stability, high mechanical resistance and high accuracy. In the frame of molten salt reactor studies, a dynamic reference electrode (DRE) is developed to measure redox potential in fluoride molten salt at high temperature. DRE is based on the in-situ generation of a transient redox system. The choice of the redox couple corresponds to the cathodic limit of the molten salt considered. As a preliminary step, the demonstration of feasibility of generating a DRE was done in LiF-NaF-KF (46.5–11.5–42 mol%) media at 500 °C. In this salt, the reference redox system generated by coulometry at applied current is KF/K, metallic potassium being electrodeposited on a tungsten wire electrode. The validation of the DRE response and the experimental optimization parameters for DRE generation were realized by following the NiF 2 /Ni redox potential evolution as a function of NiF 2 concentration in the fused salt. The current value applied for DRE generation was optimized. It depends on the amount of metallic cations contained in the fused salt and which can be electrochemically reduced simultaneously during the DRE generation. The current corresponding to the DRE generation has to be 4 times greater than the current corresponding to the reduction of the other elements.

Reference materials and interlaboratory comparison for actinide analysis

Energy Technology Data Exchange (ETDEWEB)

Hanssens, Alain; Viallesoubranne, Carole; Roche, Claude; Liozon, Gerard [Commissariat a l' Energie Atomique, Marcoule: BP 17171, 30207 Bagnols sur Ceze (France)

2008-07-01

Measurement quality is crucial for the safety of nuclear facilities and is a primary requirement for fissile material monitoring and accountancy. CETAMA (Cea Committee for the establishment of analysis methods), in collaboration with Cea and AREVA laboratories, fabricates certified reference materials and organizes interlaboratory comparison programs for plutonium and uranium assay in solution. A new plutonium metal measurement standard (MP3) is currently being prepared by Cea and is a subject of cooperative work in view of its certification and use by analysis laboratories. U and Pu interlaboratory comparisons are carried out at regular intervals on benchmark samples in coordination with working groups from French nuclear laboratories. These programs are supported by international cooperation. 'Chemical' methods (potentiometry, gravimetric analysis, etc.) generally provide the best accuracy. Coulometry is the benchmark technique for plutonium assay: its metrological qualities should be an incentive for wider use by laboratories performing precise control assays of plutonium as well as uranium. Gravimetric analysis provides excellent results for analysis of pure uranyl nitrate solutions. In view of its many advantages we encourage laboratories to employ this technique to assay pure U or Pu solutions. 'Physical' or 'physicochemical' methods are increasingly used, and their performance has improved. K-edge absorption spectrometry and isotope dilution mass spectrometry are capable of reaching measurement quality levels comparable to those of the best 'chemical' methods. (authors)

Electrooxidation of borohydride on platinum and gold electrodes: implications for direct borohydride fuel cells

Energy Technology Data Exchange (ETDEWEB)

Gyenge, E. [University of British Columbia, Vancouver (Canada). Dept. of Chemical and Biological Engineering

2004-03-01

The electrochemical oxidation of BH{sub 4}{sup -} in 2M NaOH on Pt and Au (i.e. catalytic and non-catalytic electrodes, respectively, for BH{sub 4}{sup -} hydrolysis accompanied by H{sub 2} evolution) has been studied by cyclic voltammetry, chrono-techniques (i.e., potentiometry, amperometry, coulometry) and electrochemical impedance spectroscopy. In the case of Pt the cyclic voltammetry behaviour of BH{sub 4}{sup -} is influenced by both, the catalytic hydrolysis of BH{sub 4}{sup -} yielding H{sub 2} followed by electrooxidation of the latter at peak potentials between -0.7 and -0.9 V versus Ag/AgCl, KCl{sub std} and direct oxidation of BH{sub 4}{sup -} at more positive potentials, i.e., between -0.15 and -0.05 V. Thiourea (TU, 1.5 x 10{sup -3} M) was an effective inhibitor of the catalytic hydrolysis associated with BH{sub 4}{sup -} electrooxidation on Pt. Therefore, in the presence of TU, only the direct oxidation of BH{sub 4}{sup -} has been detected, with peak potentials between -0.2 and 0 V. It is proposed that TU could improve the BH{sub 4}{sup -} utilization efficiency and the coulombic efficiency of direct borohydride fuel cells using catalytic anodes. The electrooxidation of BH{sub 4}{sup -} on Pt/TU is an overall four-electron process, instead of the maximum eight electrons reported for Au, and it is affected by adsorbed species such as BH{sub 4}{sup -} (fractional surface coverage {approx}0.3), TU and possibly reaction intermediates. (author)

An analytical laboratory to facilitate international safeguards

International Nuclear Information System (INIS)

Clark, B.E.; Muellner, P.; Deron, S.

1976-01-01

Member States which have concluded safeguards agreements accept safeguards on part or all of their nuclear facilities and nuclear materials. The Agreements enable the Agency to make inspections in order to verify the location, identity, quantity and composition of all safeguarded nuclear material. The independent analysis of samples of safeguards material is an essential part of the verification process. A new analytical laboratory has been made available to the Agency by the Austrian Government. This facility is staffed by the Agency with scientists and technicians from five Member States. Design criteria for the laboratory were defined by the Agency. Construction was carried out under the project management of the Oesterreichische Studiengesellschaft fuer Atomenergie Ges.m.b.H. Scientific equipment was procured by the Agency. Samples of feed and product material from the nuclear fuel cycle will constitute the main work load. Irradiated and unirradiated samples of uranium, plutonium and mixtures of both will be analysed for concentration and isotopic composition. Since highly diluted solutions of spent fuel will be the most active beta-gamma samples, shielded and remote manipulation facilities are not necessary. Ptentiometry, mass spectrometry and coulometry are the main techniques to be employed. Gravimetry, alpha and gamma spectrometry and emission spectroscopy will also be utilized as required. It is not intended that this laboratory, should carry the whole burden of the Agency's safeguards analytical work, but that it should function as a member of a network of international laboratories which has been set up by the Agency for this purpose. (author)

Epinephrine increases contextual learning through activation of peripheral β2-adrenoceptors.

Science.gov (United States)

Alves, Ester; Lukoyanov, Nikolay; Serrão, Paula; Moura, Daniel; Moreira-Rodrigues, Mónica

2016-06-01

Phenylethanolamine-N-methyltransferase knockout (Pnmt-KO) mice are unable to synthesize epinephrine and display reduced contextual fear. However, the precise mechanism responsible for impaired contextual fear learning in these mice is unknown. Our aim was to study the mechanism of epinephrine-dependent contextual learning. Wild-type (WT) or Pnmt-KO (129x1/SvJ) mice were submitted to a fear conditioning test either in the absence or in the presence of epinephrine, isoprenaline (non-selective β-adrenoceptor agonist), fenoterol (selective β2-adrenoceptor agonist), epinephrine plus sotalol (non-selective β-adrenoceptor antagonist), and dobutamine (selective β1-adrenoceptor agonist). Catecholamines were separated by reverse-phase HPLC and quantified by electrochemical detection. Blood glucose was measured by coulometry. Re-exposure to shock context induced higher freezing in WT and Pnmt-KO mice treated with epinephrine and fenoterol than in mice treated with vehicle. In addition, freezing response in Pnmt-KO mice was much lower than in WT mice. Freezing induced by epinephrine was blocked by sotalol in Pnmt-KO mice. Epinephrine and fenoterol treatment restored glycemic response in Pnmt-KO mice. Re-exposure to shock context did not induce a significant difference in freezing in Pnmt-KO mice treated with dobutamine and vehicle. Aversive memories are best retained if moderately high plasma epinephrine concentrations occur at the same moment as the aversive stimulus. In addition, epinephrine increases context fear learning by acting on peripheral β2-adrenoceptors, which may induce high levels of blood glucose. Since glucose crosses the blood-brain barrier, it may enhance hippocampal-dependent contextual learning.

New Signal Readout Principle for Solid-Contact Ion-Selective Electrodes.

Science.gov (United States)

Vanamo, Ulriika; Hupa, Elisa; Yrjänä, Ville; Bobacka, Johan

2016-04-19

A novel approach to signal transduction concerning solid-contact ion-selective electrodes (SC-ISE) with a conducting polymer (CP) as the solid contact is investigated. The method presented here is based on constant potential coulometry, where the potential of the SC-ISE vs the reference electrode is kept constant using a potentiostat. The change in the potential at the interface between the ion-selective membrane (ISM) and the sample solution, due to the change in the activity of the primary ion, is compensated with a corresponding but opposite change in the potential of the CP solid contact. This enforced change in the potential of the solid contact results in a transient reducing/oxidizing current flow through the SC-ISE. By measuring and integrating the current needed to transfer the CP to a new state of equilibrium, the total cumulated charge that is linearly proportional to the change of the logarithm of the primary ion activity is obtained. In this work, different thicknesses of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrenesulfonate) (PSS) were used as solid contact. Also, coated wire electrodes (CWEs) were included in the study to show the general validity of the new approach. The ISM employed was selective for K(+) ions, and the selectivity of the membrane under implementation of the presented transduction mechanism was confirmed by measurements performed with a constant background concentration of Na(+) ions. A unique feature of this signal readout principle is that it allows amplification of the analytical signal by increasing the capacitance (film thickness) of the solid contact of the SC-ISE.

How well can we measure U and Pu on an interlaboratory basis?

International Nuclear Information System (INIS)

De Bievre, P.; Mayer, K.

1991-01-01

In measurements in general, and nuclear measurements in particular, it is no more a secret that the real state-of-the-practice (SOP) is frequently different from what is said at Conferences, written in books or claimed in meetings. Frequently the latter refer to the state-of-the-art (SOA) in research laboratories or to the ultimate possible only achievable in a few highly specialized institutes. Since it is important to have an objective basis to determine where the authors stand in SOP, CBNM is running a program to regularly determine the SOP on an interlaboratory basis for U and Pu element and isotope assay: REIMEP (Regular European Interlaboratory Measurement Evaluation Program). Participation is open to non-European countries. Well characterized samples are distributed to participants with characteristics undisclosed until participants' measurements have been received. Subsequently pictures are provided displaying (a) the interlaboratory spread, (b) the deviation of each participant to the carefully characterized reference value, (c) the participant's own estimate of his uncertainty allowing comparison with other participant's uncertainties and the uncertainty of the reference value. Thus the pictures act as instant photographs (snapshots) of the real SOP. The choice of the analytical method is up to the participant (titrimetry, coulometry, α-spectrometry, gas mass spectrometry, γ-spectrometry, thermionic mass spectrometry,...). The quoted uncertainty is also the participant's choice, but should be an accuracy defined as an uncertainty range claiming, for all practical purposes, to contain the true value. Up to now a number of rounds have been performed on various U and/or Pu containing materials such as pellets, powders, solutions, UF 6 . A number of graphs displaying the SOP will be shown

Electrochemistry of oxo-technetium(V) complexes containing Schiff base and 8-quinolinol ligands

International Nuclear Information System (INIS)

Refosco, F.; Mazzi, U.; Deutsch, E.; Kirchhoff, J.R.; Heineman, W.R.; Seeber, R.

1988-01-01

The electrochemistry of six-coordinate, monooxo technetium(V) complexes containing Schiff base ligands has been studied in acetonitrile and N,N'-dimethylformamide solutions. The complexes have the general formula TcOCl(L B ) 2 or TcO(L T )(L B ), where L B represents a bidentate-N,O Schiff base ligand or a bidentate-N,O 8-quinolinol ligand and L T represents a tridentate-O,N,O Schiff base ligand. Cyclic voltammetry at a platinum-disk electrode, controlled-potential coulometry, and thin-layer spectroelectrochemistry were used to probe both the oxidation and the reduction of these complexes. The results of these studies, and previously reported results on the analogous Re(V) complexes, can be understood within a single general reaction scheme. The salient features of this scheme are (i) one-electron reduction of Tc(V) to Tc(IV), (ii) subsequent loss of a ligand situated cis to the Tc≡O linkage, and (iii) subsequent isomerization of this unstable Tc(IV) product to more stable complex in which the site trans to the Tc≡O linkage is vacant. The Tc(IV) complexes can also be reduced to analogous Tc(III) species, which appear to undergo the same ligand loss and isomerization reactions. The technetium complexes are 400-500 mV easier to reduce than are their rhenium analogues. The 8-quinolinol ligands, and especially the 5-nitro derivative, both thermodynamically and kinetically stabilize the Tc(IV) and Tc(III) oxidation states. These electrogenerated species are unusual in that they constitute the bulk of the known examples of monomeric Tc(IV) and Tc(III) complexes containing only N- and O-donating ligands. 34 refs., 9 figs., 1 tab

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes

International Nuclear Information System (INIS)

Le Bozec, N.

2000-01-01

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

Energy Technology Data Exchange (ETDEWEB)

Le Bozec, N

2000-01-15

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

Energy Technology Data Exchange (ETDEWEB)

Le Bozec, N

2000-01-15

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

Effects of warming, acidification, and reef-zone on the calcification of four Caribbean scleractinian corals of the Belize Barrier Reef System

Science.gov (United States)

Bove, C. B.; Ries, J. B.; Davies, S. W.; Westfield, I. T.; Castillo, K.

2016-02-01

Rising atmospheric carbon dioxide (pCO2) has caused ocean temperature to increase and ocean pH to decrease, raising concerns about the health of marine organisms. Previous studies have shown that corals are particularly vulnerable to these stressors, most likely due to their narrow thermal tolerance and use of carbonate ions in calcification, although response patterns vary across taxa. We conducted laboratory experiments for 95 days to investigate the independent and interactive effects of ocean warming (28, 31 °C) and acidification on the calcification rate and skeletal properties of four abundant and ubiquitously distributed Caribbean coral species (Pseudodiploria strigosa, Siderastrea siderea, Porites astreoides, Undaria tenuifolia) collected from nearshore and forereef environments of the Belize Barrier Reef. Aragonite saturation states of 3.9, 3.2, 2.2, and 0.7, constrained by total alkalinity measured via closed-cell potentiometric titration and dissolved inorganic carbon measured via coulometry, were attained by sparging natural seawater with air-CO2 mixtures formulated at 280, 400, 700, and 2800 ppmv pCO2, respectively. Temperature and pCO2 were fully crossed (N=3 tanks per treatment) and corals were gradually exposed to treatment conditions over a 30-day period, followed by an additional 30-day acclimation. Rates of linear skeletal extension were measured relative to a calcein spike emplaced in the coral skeletons at the start of the experiment, and net calcification rates were determined from coral buoyant weights obtained every 30 days. Initial results show that corals in all treatments continued to calcify on a net basis, however, the effect of warming on net calcification rates of P. asteroids and U. tenuifolia became more negative at lower saturation states. In addition, nearshore U. tenuifolia calcified faster than forereef conspecifics in all treatments.

NEW INSIGTHS ON THE KINETICS AND MECHANISM OF THE ELECTROCHEMICAL OXIDATION OF DICLOFENAC IN NEUTRAL AQUEOUS MEDIUM

International Nuclear Information System (INIS)

Cid-Cerón, M.M.; Guzmán-Hernández, D.S.; Ramírez-Silva, M.T.; Galano, A.; Romero-Romo, M.; Palomar-Pardavé, M.

2016-01-01

Highlights: • DCF electrochemical oxidation was studied from aqueous solution with a CPE. • Both stagnant and forced convection conditions were considered. • We found DCF electrochemical oxidation is a mass transfer-controlled process. • An EC mechanism was found where the electrodic is quasi-reversible. • C reaction provokes the breaking up the DCF through the nitrogen atom. • DCF diffusion coefficient was experimental and theoretically calculated. - Abstract: The diclofenac (DCF) electrochemical oxidation mechanism was studied through: linear voltammetry (LV), chronoamperometry (CA) sampled-current voltammetry (SCV), potentiostatic coulometry (PC) cyclic voltammetry (CV) under stagnant conditions and linear voltammetry under forced convection conditions (FCLV) over a carbon paste electrode (CPE) from an aqueous medium containing 0.1 M phosphate buffer at pH 7. It was found that the DCF electrochemical oxidation involves an EC mechanism, where the electrochemical reaction is carried out through a one electron-exchange while the chemical reaction involves breaking up the DCF through the nitrogen atom, thereby generating the fragments 2,6 dichloroaniline and 2-(2hydroxyprop-2-enyl)phenol. Reverting the potential scan in the cathodic direction at different scan rates and regardless of its rate, after the oxidation peak, it was found that it was possible to reduce only 38% of the DCF oxidized. The spectrophotometric study carried out during different macro-electrolysis periods allowed observing that the current decrease of the oxidation peak coupled to the DCF absorption (at 270 nm), together with the development of a new spectrophotometric absorption maximum (450 nm), all confirm the EC mechanism proposed. With the use of several experimental techniques (CA, LV and FCLV) and theoretical ones using the Stokes–Einstein approach, the DCF diffusion coefficient was determined, this being in average 8.1 × 10"−"6 cm"2 s"−"1.

O/M ratio measurement in pure and mixed oxide fuels - where are we now?

Energy Technology Data Exchange (ETDEWEB)

Rubin, J.; Chidester, K.; Thompson, M. [Los Alamos National Lab., NM (United States)

2001-07-01

The scale-down in the US and Russian nuclear weapons stockpiles has produced a surplus of weapons grade plutonium and highly enriched uranium. The incorporation into mixed-oxide fuel (MOX) is one of the currently favored routes for surplus weapons-grade plutonium. The use of MOX as a nuclear reactor fuel is well established, particularly in Europe and Japan but not in the US. The primary purpose of this investigation was to evaluate existing analytical techniques for their applicability to O/M (oxygen-to-metal ratio) measurements of MOX derived from excess weapons plutonium. The second objective of this investigation was to bring up-to-date the literature on O/M measurement methods, which has not been undertaken in over 20 years. There are several classification schemes that can be used to organize O/M measurement methods. The most popular schemes are based on (a) whether the analysis is performed in solution (wet chemical) or on solid material (dry), and (b) whether the concentration of major constituents are analyzed directly (direct) or are inferred (indirect). Solid state coulometric titration is currently used extensively in studies of phase equilibria, defect chemistry, thermochemical measurement of oxides, including ferrites. Regardless of which indirect method is used (solid state coulometric titration or thermogravimetry), a primary, direct method will also be required for the establishment of the MO{sub 2} reference state, determination of method bias, and periodic calibration. It was recommended that the following direct method be adapted for this purpose: oxygen measurement by inert gas fusion/carbon reduction, and total U, Pu by controlled potential coulometry. In a table are listed the experimental values of accuracy for about 30 O/M methods. (A.C.)

Rock magnetic signature of paleoenvironmental changes in the Izu Bonin rear arc over the last 1 Ma

Science.gov (United States)

Kars, Myriam; Vautravers, Maryline; Musgrave, Robert; Kodama, Kazuto

2015-04-01

During April and May 2014, IODP Expedition 350 drilled a 1806.5 m deep hole at Site U1437 in the Izu-Bonin rear arc, in order to understand, among other objectives, the compositional evolution of the arc since the Miocene and track the missing half of the subduction factory. The good recovery of mostly fine grained sediments at this site enables a high resolution paleontological and rock magnetic studies. Particularly, variations in magnetic properties and mineralogy are well documented. Natural remanent magnetization and magnetic susceptibility vary with a saw-tooth pattern. Routine rock magnetic measurements performed on about 400 samples in the first 120 meters of Hole U1437B showed that pseudo single domain to multidomain magnetite is the main carrier of the remanence. The origin of magnetite is likely detrital. The magnetic susceptibility variations depend on many factors (e.g. lithology, magnetic mineralogy, and also dilution by the carbonate matrix). The magnetic susceptibility is also used as a proxy, at first order, for magnetic minerals concentration. In order to highlight changes in magnetic minerals concentration, it's necessary to correct for the carbonate dilution effect. Onboard and onshore carbonate measurements by coulometry show that the carbonate content of the samples can be up to ~60%. About 70 samples were measured onshore. After correcting the susceptibility by the carbonate content measured on the same samples, it appears that the pattern of the magnetic susceptibility before and after correction is similar. Then the magnetic susceptibility variations do not result from carbonate dilution but reflect fluctuating influx of the detrital sediment component. The delta O18 variations obtained on foraminifers (N. dutertrei) show MIS 1 to MIS 25 over the studied interval covering the last 1 Ma (see Vautravers et al., this meeting). Rock magnetic properties, concentration and grain size variations of the magnetic minerals will be compared to

A Novel Method for Analysis of Dissolved Inorganic Carbon Concentration and δ13C by Cavity Ring-Down Spectroscopy

Science.gov (United States)

Smith, E.; Gonneea, M. E.; Boze, L. G.; Casso, M.; Pohlman, J.

2017-12-01

Dissolved inorganic carbon (DIC) is the largest pool of carbon in the oceans and is where about half of anthropogenic carbon dioxide (CO2) emissions are being sequestered. Determining the concentration and stable carbon isotopic content (δ13C) of DIC allows us to delineate carbon sources that contribute to marine DIC. A simple and reliable method for measuring DIC concentration and δ13C can be used to apportion contributions from external sources and identify effects from biogeochemical reactions that contribute or remove DIC. The U.S. Geological Survey has developed a discrete sample analysis module (DSAM) that interfaces to a Picarro G-2201i cavity ring-down spectrometer (CRDS, Picarro Inc.) to analyze CO2 and methane concentrations and δ13C from discrete gas samples. In this study, we adapted the USGS DSAM-CRDS analysis system to include an AutoMate prep device (Automate FX, Inc.) for analysis of DIC concentration and δ13C from aqueous samples. The Automate prep device was modified to deliver CO2 extracted from DIC to the DSAM, which conditions and transfers the gas to the CRDS. LabVIEW software (National Instruments) triggers the Automate Prep device, controls the DSAM and collects data from the CRDS. CO2 mass concentration data are obtained by numerical integration of the CO2 volumetric concentrations output by the CRDS and subsequent comparison to standard materials. CO2 carbon isotope values from the CRDS (iCO2) are converted to δ13C values using a slope and offset correction calibration procedure. The system design and operation was optimized using sodium bicarbonate (NaHCO3) standards and a certified reference material. Surface water and pore water samples collected from Sage Lot Pond, a salt marsh in Cape Cod MA, have been analyzed for concentration by coulometry and δ13C by isotope ratio mass spectrometry and will be used to validate the DIC-DSAM-CRDS method for field applications.

Detection, characterization and quantification of inorganic engineered nanomaterials: A review of techniques and methodological approaches for the analysis of complex samples

Energy Technology Data Exchange (ETDEWEB)

Laborda, Francisco, E-mail: flaborda@unizar.es; Bolea, Eduardo; Cepriá, Gemma; Gómez, María T.; Jiménez, María S.; Pérez-Arantegui, Josefina; Castillo, Juan R.

2016-01-21

The increasing demand of analytical information related to inorganic engineered nanomaterials requires the adaptation of existing techniques and methods, or the development of new ones. The challenge for the analytical sciences has been to consider the nanoparticles as a new sort of analytes, involving both chemical (composition, mass and number concentration) and physical information (e.g. size, shape, aggregation). Moreover, information about the species derived from the nanoparticles themselves and their transformations must also be supplied. Whereas techniques commonly used for nanoparticle characterization, such as light scattering techniques, show serious limitations when applied to complex samples, other well-established techniques, like electron microscopy and atomic spectrometry, can provide useful information in most cases. Furthermore, separation techniques, including flow field flow fractionation, capillary electrophoresis and hydrodynamic chromatography, are moving to the nano domain, mostly hyphenated to inductively coupled plasma mass spectrometry as element specific detector. Emerging techniques based on the detection of single nanoparticles by using ICP-MS, but also coulometry, are in their way to gain a position. Chemical sensors selective to nanoparticles are in their early stages, but they are very promising considering their portability and simplicity. Although the field is in continuous evolution, at this moment it is moving from proofs-of-concept in simple matrices to methods dealing with matrices of higher complexity and relevant analyte concentrations. To achieve this goal, sample preparation methods are essential to manage such complex situations. Apart from size fractionation methods, matrix digestion, extraction and concentration methods capable of preserving the nature of the nanoparticles are being developed. This review presents and discusses the state-of-the-art analytical techniques and sample preparation methods suitable for

Detection, characterization and quantification of inorganic engineered nanomaterials: A review of techniques and methodological approaches for the analysis of complex samples

International Nuclear Information System (INIS)

Laborda, Francisco; Bolea, Eduardo; Cepriá, Gemma; Gómez, María T.; Jiménez, María S.; Pérez-Arantegui, Josefina; Castillo, Juan R.

2016-01-01

The increasing demand of analytical information related to inorganic engineered nanomaterials requires the adaptation of existing techniques and methods, or the development of new ones. The challenge for the analytical sciences has been to consider the nanoparticles as a new sort of analytes, involving both chemical (composition, mass and number concentration) and physical information (e.g. size, shape, aggregation). Moreover, information about the species derived from the nanoparticles themselves and their transformations must also be supplied. Whereas techniques commonly used for nanoparticle characterization, such as light scattering techniques, show serious limitations when applied to complex samples, other well-established techniques, like electron microscopy and atomic spectrometry, can provide useful information in most cases. Furthermore, separation techniques, including flow field flow fractionation, capillary electrophoresis and hydrodynamic chromatography, are moving to the nano domain, mostly hyphenated to inductively coupled plasma mass spectrometry as element specific detector. Emerging techniques based on the detection of single nanoparticles by using ICP-MS, but also coulometry, are in their way to gain a position. Chemical sensors selective to nanoparticles are in their early stages, but they are very promising considering their portability and simplicity. Although the field is in continuous evolution, at this moment it is moving from proofs-of-concept in simple matrices to methods dealing with matrices of higher complexity and relevant analyte concentrations. To achieve this goal, sample preparation methods are essential to manage such complex situations. Apart from size fractionation methods, matrix digestion, extraction and concentration methods capable of preserving the nature of the nanoparticles are being developed. This review presents and discusses the state-of-the-art analytical techniques and sample preparation methods suitable for

Burn up physics

International Nuclear Information System (INIS)

Tretiakoff, O.

1964-01-01

The present communication is devoted to a body of theoretical and experimental work carried out at the C.E.A. with the aim of adding to the current knowledge on the evolution of the reactivity (during fuel irradiation) in natural or slightly enriched Uranium reactors. The difficulties of performing direct experiments on large amounts of irradiated fuels are reviewed - especially in operating power reactors - and the necessity is underlined for fundamental research in two directions: on one hand, the change in the composition of the fuels (chains of heavy nuclei, fission products), and on the other hand the effect of changes in composition on the neutron balance. Before presenting three types of experiments which have been carried out, the importance of the problems associated with the neutron spectra is stressed and the practical methods used for the calculations are briefly described. The systematic irradiation of several types of fuel, followed by their chemical and isotopic analysis has been going on for several years. An outline of the experimental programme is given with a description of the methods employed: α, β, γ chain for the preparation of samples determination of the plutonium content by coulometry and double isotopic dilution, separation of Boron used in some cases for the measurement of integrated neutron densities. The interpretation of the measurements is discussed with some examples. A second and more recent series of experiments deals with the investigation of lattices, using synthetic fuels (Uranium-Plutonium alloys) as compared to slightly depleted or enriched Uranium Various experiments are considered on heavy water and on cold graphite, then on graphite heated up to 500 C Some results already obtained are listed. These experiments, requiring nearly a metric ton of each type of fuel cannot be pursued in a systematic manner. This is why is developed since several years a method of differential measurement by oscillation, which requires

PHOTO-ELECTROCHEMICAL QUANTUM EFFICIENCY OF TiO2 THIN FILMS : EFFECT OF CRISTAL STRUCTURE, PLASMA HYDROGENATION AND SURFACE PHOTOETCHING

Directory of Open Access Journals (Sweden)

E TEYAR

2007-12-01

Full Text Available The use of semi-conducting materials in the photoelectrochemical detoxification of water became a very important research field. For this purpose, TiO2 nanostructures thin films with size of 18 nm to 45nm have been synthesized at low temperature. It is found by means of cyclic voltametry and coulometry measurements that the best photoelectrochemical quantum efficiency under UV monochromatic light with a wavelength of 365 nm and a solution of NaOH 0.1N is obtained in the case of thermal oxidation deposition method which can reach 28% compared to ultrasonic spray and dip coating methods of which the quantum is less than 20%. The crystal structure has an influence on the photo-degradation of methanol. The crystal structure which is recommended for this task is the anatase one, especially in the dipping case when the quantum increases after addition of methanol more than twice compared to the solution of NaOH without methanol. The photoelectrochemical quantum efficiency of these films is related to the number of dips and annealing under air at 550°C during one hour. The annealing has no effect on the quantum efficiency of the films, but decreases there photocatalytic activity as showed by the measure of the photocurrent related to methanol photodegradation. The annealing has no effect on the crystal structure of the material. The impedance spectroscopy of six dips deposited films with and without methanol shows that the annealing increases the doping and weakly decreases the film quantum efficiency. This implies, the importance of surface morphology which the rough is decreasing as showed by scanning electron microscopy. The effect of the precursor concentration in ethanol have been investigated by using films, synthesized at T=550°C. The quantum efficiency increases weakly according the precursor concentration. It tends towards a saturation at great concentrations of precursor. In Na OH with methanol added, it passes by a maximum at

Utilización de técnicas acopladas de análisis térmico TG-DSC-QMSFTIR en la caracterización de arcillas y composiciones cerámicas utilizadas en la fabricación de baldosas cerámicas. Cuantificación de compuestos de carbono

Directory of Open Access Journals (Sweden)

Gómez, M. P.

2007-10-01

Full Text Available In this study, a work methodology has been developed for t evolved gas analysis (EGA in clay raw materials and ceramic compositions used in ceramic tile manufacture using coupled thermal analysis techniques (TG-DSC-QMS-FTIR. The different types of gases (CO2, CO, NOx, F, SOx evolving from these raw materials during a thermal cycle up to a peak temperature of 1200ºC were characterised. The possibility of using this calorimeter for the quantification of the CO2 gases evolving from the organic and inorganic carbon (carbonates present in the studied clay materials was also evaluated. The measurements were validated with different reference materials, and the results were compared with those obtained with other analysis techniques, such as thermogravimetry (TG, calcimetry, and coulometry. The thermal analysis technique (TG-DSC-QMS-FTIR is a suitable technique for analysing evolved gases with low uncertainties for carbon compounds quantification. Furthermore, the methodology allows the mineralogical origin identification of the elements present in the evolved gases.

En el presente estudio se ha desarrollado una metodología de trabajo para el análisis de emisiones gaseosas (EGA en materias primas arcillosas y composiciones cerámicas utilizadas en la fabricación de baldosas cerámicas mediante técnicas acopladas de análisis térmico (TG-DSC-QMS-FTIR. Se caracterizaron los distintos tipos de emisiones (CO2, CO, NOx, F, SOx que se emiten durante un ciclo térmico hasta una temperatura máxima de 1200ºC. Asimismo, se evaluó la posibilidad de la utilización de la técnica para la cuantificación de dichas emisiones. En concreto se ha realizado la cuantificación de emisiones de CO2 procedentes de la presencia de carbono orgánico e inorgánico en materiales arcillosos. Se han validado las medidas con distintos materiales de referencia y se han comparado los resultados con los obtenidos con otras técnicas de análisis, tales como la

Calcification rates of the Caribbean reef-building coral Siderastrea siderea adversely affected by both seawater warming and CO2-induced ocean acidification

Science.gov (United States)

Horvath, K. M.; Connolly, B. D.; Westfield, I. T.; Chow, E.; Castillo, K. D.; Ries, J. B.

2013-05-01

The Intergovernmental Panel on Climate Change (IPCC) predicts that atmospheric pCO2 will increase to ca. 550-950 ppm by the end of the century, primarily due to the anthropogenic combustion of fossil fuels, deforestation, and cement production. This is predicted to cause SST to increase by 1-3 °C and seawater pH to decrease by 0.1-0.3 units. Laboratory studies have shown that warming depresses calcification rates of scleractinian corals and that acidification yields mixed effects on coral calcification. With both warming and ocean acidification predicted for the next century, we must constrain the interactive effects of these two CO2-induced stressors on scleractinian coral calcification. Here, we present the results of experiments designed to assess the response of the scleractinian coral Siderastrea siderea to both ocean warming and acidification. Coral fragments (12/tank) were reared for 60 days under three temperatures (25.1± 0.02 °C, 28.0± 0.02 °C, 31.8± 0.02 °C) at near modern pCO2 (436 ± 7) and near the highest IPCC estimate for atmospheric pCO2 for the year 2100 AD (883 ± 16). Each temperature and pCO2 treatment was executed in triplicate and contained similarly sized S. Siderea fragments obtained from the same suite of coral colonies equitably distributed amongst the nearshore, backreef, and forereef zones of the Mesoamerican Barrier Reef System off the coast of southern Belize. Individual coral fragments were hand fed Artemia sp. to satiation twice weekly. Weekly seawater samples (250 ml) were collected and analyzed for dissolved inorganic carbon via coulometry and total alkalinity via closed-cell potentiometric titration. Seawater pCO2, pH, carbonate ion concentration, bicarbonate ion concentration, aqueous CO2, and aragonite saturation state (ΩA) were calculated with the program CO2SYS. Under near-modern atmospheric pCO2 of ca. 436 ± 7 ppm, seawater warming from 25 to 28 to 32°C caused coral calcification rates (estimated from change in

Metal electrodeposition and electron transfer studies of uranium compounds in room temperature ionic liquids

International Nuclear Information System (INIS)

Stoll, M.E.; Oldham, W.J.; Costa, D.A.

2004-01-01

electrochemical methods including cyclic and square-wave voltammetry, chronoamperometry, and bulk coulometry. Results from these studies will be presented to show the general electron transfer behavior of metal complexes in the RTIL's. As an example, Figure 2 shows the difference in chemical stability of an electrogenerated U(V) anion for two uranyl (U(VI)O 2 2+ ) complexes due to the difference in ancillary ligands about the uranyl moiety. Figure 2a shows a cyclic voltammogram (CV) for the U(VI)/U(V) couple of a uranyl complex containing a multi-dentate chelating nitrogen/oxygen ligand (inset in figure). The couple is both chemically and electrochemically reversible. The CV in Figure 2b is that of [UO 2 Cl 4 ] 2- in which the electrogenerated U(V) derivative is unstable yielding a chemically irreversible wave. For the compound giving rise to the CV in Figure 2a its electrochemical behavior in a conventional nonaqueous electrolyte medium is very similar to that obtained in the RTIL. While this result does not illustrate a distinct advantage for employing the RTIL solvent in this particular case, we believe it effectively demonstrates the ability of the RTIL to be utilized as a solvent/electrolyte medium for detailed electrochemical studies without severe limitations.

Elements in human serum—CCQM-K139

Science.gov (United States)

Shin, Richard; Dewi, Fransiska; Tong, Benny; Wah, Leung Ho; Saxby, David; Armishaw, Paul; Ivanova, Veronika; Feng, Liuxing; Wang, Jun; Estela del Castillo Busto, M.; Fisicaro, Paola; Rienitz, Olaf; Fung, Wai-Hong; Ho-pan Yau, Michael; Yim, Yong-Hyeon; Buzoianu, Mirella; Can, Suleyman Z.; Ari, Betul; Cankur, Oktay; Goenaga Infante, Heidi; Pérez-Zambra, Ramiro; Ferreira, Elizabeth; Long, Stephen

2018-01-01

. Inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES) were the two most commonly used instrumental techniques. Other techniques used included ion chromatography (IC), flame atomic absorption spectrometry (FAAS), titration and micro-coulometry. The medians were used as the estimators of Key Comparison Reference Values (KCRVs) for all measurands. The KCRVs (+/- standard uncertainty) for Na, Cl, Cu, Se and P (in mg/kg) were 3346 (+/- 14), 3871 (+/- 22), 1.151 (+/- 0.007), 0.1292 (+/- 0.0007) and 125.70 (+/- 0.35), respectively. The k-factor of 2 was used for the estimation of the expanded uncertainties of the KCRVs. The degree of equivalence and its associated uncertainty were calculated for each submitted result. For the five measurands, most participating institutes were able to demonstrate their capabilities in the determination of elements in human serum. CMC claims based on elements covered in this study may include other elements with similar core competencies, such as zinc (Zn), potassium (K), magnesium (Mg), calcium (Ca) and iron (Fe), in a wide range of biological materials. The measurands should be at similar concentration range and analysed using the same measurement technique(s) applied in this key comparison. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Burn up physics; Physique des combustibles irradies

Energy Technology Data Exchange (ETDEWEB)

Tretiakoff, O [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1964-07-01

The present communication is devoted to a body of theoretical and experimental work carried out at the C.E.A. with the aim of adding to the current knowledge on the evolution of the reactivity (during fuel irradiation) in natural or slightly enriched Uranium reactors. The difficulties of performing direct experiments on large amounts of irradiated fuels are reviewed - especially in operating power reactors - and the necessity is underlined for fundamental research in two directions: on one hand, the change in the composition of the fuels (chains of heavy nuclei, fission products), and on the other hand the effect of changes in composition on the neutron balance. Before presenting three types of experiments which have been carried out, the importance of the problems associated with the neutron spectra is stressed and the practical methods used for the calculations are briefly described. The systematic irradiation of several types of fuel, followed by their chemical and isotopic analysis has been going on for several years. An outline of the experimental programme is given with a description of the methods employed: {alpha}, {beta}, {gamma} chain for the preparation of samples determination of the plutonium content by coulometry and double isotopic dilution, separation of Boron used in some cases for the measurement of integrated neutron densities. The interpretation of the measurements is discussed with some examples. A second and more recent series of experiments deals with the investigation of lattices, using synthetic fuels (Uranium-Plutonium alloys) as compared to slightly depleted or enriched Uranium Various experiments are considered on heavy water and on cold graphite, then on graphite heated up to 500 C Some results already obtained are listed. These experiments, requiring nearly a metric ton of each type of fuel cannot be pursued in a systematic manner. This is why is developed since several years a method of differential measurement by oscillation, which

Organic-Carbon Sequestration in Soil/Sediment of the Mississippi River Deltaic Plain - Data; Landscape Distribution, Storage, and Inventory; Accumulation Rates; and Recent Loss, Including a Post-Katrina Preliminary Analysis (Chapter B)

Science.gov (United States)

Markewich, Helaine W.; Buell, Gary R.; Britsch, Louis D.; McGeehin, John P.; Robbins, John A.; Wrenn, John H.; Dillon, Douglas L.; Fries, Terry L.; Morehead, Nancy R.

2007-01-01

Soil/sediment of the Mississippi River deltaic plain (MRDP) in southeastern Louisiana is rich in organic carbon (OC). The MRDP contains about 2 percent of all OC in the surface meter of soil/sediment in the Mississippi River Basin (MRB). Environments within the MRDP differ in soil/sediment organic carbon (SOC) accumulation rate, storage, and inventory. The focus of this study was twofold: (1) develop a database for OC and bulk density for MRDP soil/sediment; and (2) estimate SOC storage, inventory, and accumulation rates for the dominant environments (brackish, intermediate, and fresh marsh; natural levee; distributary; backswamp; and swamp) in the MRDP. Comparative studies were conducted to determine which field and laboratory methods result in the most accurate and reproducible bulk-density values for each marsh environment. Sampling methods included push-core, vibracore, peat borer, and Hargis1 sampler. Bulk-density data for cores taken by the 'short push-core method' proved to be more internally consistent than data for samples collected by other methods. Laboratory methods to estimate OC concentration and inorganic-constituent concentration included mass spectrometry, coulometry, and loss-on-ignition. For the sampled MRDP environments, these methods were comparable. SOC storage was calculated for each core with adequate OC and bulk-density data. SOC inventory was calculated using core-specific data from this study and available published and unpublished pedon data linked to SSURGO2 map units. Sample age was estimated using isotopic cesium (137Cs), lead (210Pb), and carbon (14C), elemental Pb, palynomorphs, other stratigraphic markers, and written history. SOC accumulation rates were estimated for each core with adequate age data. Cesium-137 profiles for marsh soil/sediment are the least ambiguous. Levee and distributary 137Cs profiles show the effects of intermittent allochthonous input and/or sediment resuspension. Cesium-137 and 210Pb data gave the most

An Appraisal of Analytical Methods for Plutonium and their Applications to the Analysis of Nuclear Materials; Evaluation des Methodes Analytiques de Dosage du Plutonium et de Leur Application a l'Analyse des Matieres Nucleaires; Otsenka analiticheskikh metodov opredeleniya plutoniya i ikh primenenie dlya analiza yadernykh materialov; Metodos Analiticos de Determinacion del Plutonio y su Empleo en el Analisis de Materiales Nucleares

Energy Technology Data Exchange (ETDEWEB)

Milner, G. W.C.; Phillips, G. [Atomic Energy Research Establishment, Harwell, Berks. (United Kingdom)

1966-02-15

A variety of methods is available for the determination of the plutonium content of nuclear materials. For milligram amounts of plutonium the available methods include differential spectrophotometry using the colour of Pu (III), gravimetry based on PuO{sub 2} gamma counting, and redox methods including potentiometric and amperometric titrations and controlled-potential coulometry. Alpha counting, isotopic dilution, and polarographic methods are suitable for microgram amounts. Some methods are more suitable than others for certain types of sample and the analyst is faced with difficult selection problems to achieve the best results. The advantages and limitations of the above methods are described in the light of a varied experience with them over many years at AERE, together with comments on accuracy, precision, sensitivity and features of special interest. Some of the methods cannot be applied without some separation of the plutonium from other sample constituents, and comments are made from experience in the use of anion exchange and reverse-phase chromatographic techniques for this with emphasis on their suitability for radioactive samples. Consideration is given to the many problems that have arisen in the successful application of these methods to the analysis of plutonium alloys, ceramics and cermets in various systems containing uranium, thorium, iron, chromium, molybdenum, cerium and cobalt. Difficulties occurring in the dissolution of samples and in the adjustment of the plutonium to the required valency state are described. The respective merits of dissolving in mixtures of common mineral acids and with the aid of fusion techniques are commented upon with examples. Outlines of procedures, together with analytical results for typical samples, are given for the analysis of Pu-U, Pu-Ce-Co and Pu-U-Mo alloys, Pu-U oxides and carbides, and Pu-U carbide cermets with Fe, Mo and Cr. These materials have arisen from metallurgical research and development